Synthetic Organic Chemistry & Materials Chemistry

376 388 Reagent Guide 8th Edition Synthetic Organic Chemistry & Materials Chemistry We have reviewed our product line-ups and organized them acc...
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388

Reagent Guide 8th Edition

Synthetic Organic Chemistry & Materials Chemistry

We have reviewed our product line-ups and organized them according to the research areas synthetic organic chemistry and materials chemistry. We hope that this reagent guide will be assistance to your research and development laboratories. However, this guide is not an all inclusive list of all the reagents we deal in. Please be sure look up our catalog and visit our website as well to remain updated on the latest information the various fields of your interest.

www.TCIchemicals.com

of of to in

Contents Synthetic Organic Chemistry “Topics”  Copper-free Click Reactions .......................................1  Easily Accessible Crystalline CO Surrogate Reagents......2 Functional Group Transformation & Introducing Reaction  Oxidation ........................................................................3  Reduction .......................................................................9  Halogenation .............................................................. 17  Trifluoromethylation ................................................... 23  Trifluoromethylthiolation ............................................ 25  Formylation ................................................................. 26  Cyanation .................................................................... 29  Amination .................................................................... 31  Mitsunobu Reaction................................................... 34  Condensation & Active Esterification ..................... 38 Carbon-Carbon Bond Forming Reactions  Carbonyl Olefination .................................................. 44  Cross-coupling Reaction Using Transition Metal Catalysts .................................................................. 52  Activation of Non-active Bonds ............................... 69 Synthetic Reagents  Metal Reagents for Organic Synthesis ................... 76  Stable Lewis Acids in Aqueous Media ................... 89  Ligands ........................................................................ 91  Asymmetric Organocatalysts .................................102  Chiral Auxiliaries ......................................................108  Chiral Phase-transfer Catalysts .............................110  Optical Resolving Agents .......................................113  Protection & Derivatization ....................................120  Ionic Liquids .............................................................130  Fluorous Solvents ....................................................135  Polymer-supported Reagents .................................137 Building Blocks  Boronic Acids & Boronic Acid Derivatives ..........139  Chiral Building Blocks.............................................156  Terminal Acetylenes ................................................180  Azide Compounds....................................................186

Materials Chemistry Nanocarbon Materials  Fullerenes .................................................................190  Carbon Nanotubes ...................................................192  Graphene & Graphene Oxide .................................194  Nanodiamonds .........................................................196  Nanocarbon Unit Structures ..................................198 Electronic Materials  Reagents for Solar Cell Research .........................201  Reagents for Secondary Battery ...........................206  Organic Light-Emitting Diode Materials ...............213  Organic Transistor Materials ..................................219  Molecular Conductors .............................................223  Building Blocks for Semiconducting Polymer .....230  Building Blocks for Small Molecule Semiconductor ...238  Ligands for Functional Metal Complex ................254 Optically Functional Materials  Photochromic Compounds .....................................259  Liquid Crystal Materials ..........................................262  Building Blocks for Liquid Crystals .......................270  Organic Nonlinear Optical Materials ....................274  Materials for Near Infrared Absorption .................276

Magnetic Materials  Magnetic Metal Complexes ...................................277  Organic Radicals .....................................................281  Magnetic Ionic Liquids ............................................283 Functional Organic Dyes  Coumarin Dyes.........................................................284  Porphyrin & Phthalocyanine Dyes ........................286  Perylene Dyes ..........................................................289  Cyanine & Squarylium Dyes ..................................291  Dipyrromethene Dyes ..............................................293  Xanthene Dyes .........................................................294  DCM Dyes ................................................................296  Quinacridone Dyes ..................................................297 Organic-Inorganic Hybrid Materials  Metal-Organic Frameworks (MOFs / PCPs) & Related Ligands.....................................................298  Organic-Inorganic Perovskite Precursors .............303  Silane Coupling Agents ..........................................305  Self-Assembled Monolayer (SAM) Forming Agents .....................................................313 Polymer Research Reagents  Polymers ...................................................................316  Monomers .................................................................319  Polymerization Inhibitors.........................................320  Polymerization Initiators..........................................321  Polymerization Catalysts ........................................325  Precise Polymerization Reagents .........................328  Resin Additives ........................................................333  Photopolymer Research Reagents ........................341 Macrocycles for Host-Guest Chemistry  Macrocycles for Host-Guest Chemistry ...............342 Other Reagents  Building Blocks for Dendrimers .............................348  Derivatizing Reagents for Solubility Improvement ...351 Abbreviations ................................................................360 Pressure-Temperature Nomograph ...........................362 The physical properties of the typical organic solvents / Freezing mixtures .....................................................363 Periodic Table of the Elements .................................364 INDEX ...........................................................................365 TCI International Offices .............................................376 TCI Distributors ............................................................377

If you are looking for products in the field of Bioscience & Analytical Science, please see below.

Reagent Guide 8th Edition Bioscience & Analytical Science Bioscience Example : Antibodies / Sugars / Nucleosides / Amino Acids / Lipids / Terpenes / Steroids etc. Analytical Science Example : GC Derivatizing Reagents / Labeling Reagents for HPLC / Chromatography Columns for HPLC / Derivatization Reagents for Mass Spectrometry etc.

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

Copper-free Click Reactions

Synthetic Organic Chemistry

Copper-free Click Reactions

Cyclooctyl group [2+3] cycloaddition with azides High reaction rate constant

H

H O O

N H

O

2

NH2

BCN-amine [B4062] H N

N O

H N O

Materials Chemistry

Among the“click chemistry”proposed by K. B. Sharpless in 2001, the Huisgen cyclization using azides and terminal alkynes has been widely used in various reseach fields such as chemical biology and material science due to its excellent chemoselectivity.1) Generally, the Huisgen cyclization requires some copper salts to promote the reactions. However, use of the copper salt-mediated click reactions for applications is often highly restricted owing to the toxicity of active oxygen generated by the copper salt. Therefore, the development of advanced click reactions without using any copper salt has been investigated. In the research fields using copper-free click reactions, a number of studies aimed for applications such as living cells and biological experiments on animals have been reported. To be suitable for such purposes, molecular design of alkyne derivatives has been performed mainly to improve two chemical properties of second order reactions, rate constant and lipophilicity (log P). In 2004, C. R. Bertozzi . have reported the copper-free click reaction using highly-strained cyclooctyl groups as reactants. These cyclooctyl compounds satisfy the above mentioned two requests and are widely used as a molecular tool to reveal the metabolic systems.2) Recently, they have been used to construct the microenvironment of hydrogels supporting the basis of regenerative medicine research. Because of that, Bertozzi . have suggested general and accessible experimental procedures for researchers who don’ t do major synthetic organic chemistry, and their practical examples can be referred to in the research article.3) Furthermore, van Delft have developed more effective cyclooctyl compounds usable for bioorthogonal and 3D imaging.3) For instance, ADIBO-amine and BCN-amine are suitable molecules for the copper-free click reaction in biological research because they have low lipophilicity and high reactivity. Especially, ADIBO-amine is used for PEGylation of proteins and nuclear imaging by positron emission tomography (PET) using a fluorine-18 [18F] radioisotope. As stated above, ADIBO-amine and BCN-amine are expected to be powerful versatile tools for the copper-free click reaction because they can also be used for surface reforming of solid materials and chemical modification of organic molecules in material science research as well as live imaging and microarray analysis in life science research.

O

Amino group Easy to modify NH2

O 2

ADIBO-amine [A2607]

Product No.

Product Name

A2607

9,15-Diaza-18-DBCO-3,6-dioxa-10,14,18-trioxooctadecylamine (ADIBO-amine) N-(1R,8S,9s)-Bicyclo[6.1.0]non-4-yn-9-ylmethyloxycarbonyl1,8-diamino-3,6-dioxaoctane (BCN-amine)

B4062

Unit Size

25mg 25mg

100mg

References 1) 2) 3) 4)

H. C. Kolb, M. G. Finn, K. B. Sharpless, . 2001, , 2004. N. J. Agard, J. A. Prescher, C. R. Bertozzi, . 2004, , 15046. E. M. Sletten, C. R. Bertozzi, . 2011, , 666. a) J. Dommerholt, S. Schmidt, R. Temming, L. J. A. Hendriks, F. P. J. T. Rutjes, J. C. M. van Hest, D. J. Lefeber, P. Friedl, F. L. van Delft, . 2010, , 9422. b) M. F. Debets, S. S. van Berkel, S. Schoffelen, F. P. J. T. Rutjes, J. C. M. van Hest, F. L. van Delft, . 2010, , 97.

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

1

Easily Accessible Crystalline CO Surrogate Reagents

Synthetic Organic Chemistry

Easily Accessible Crystalline CO Surrogate Reagents Carbon monoxide (CO) is used as a significant carbonyl group-introducing reagent in organic synthesis. A number of synthetic reactions using CO have been developed. Because CO is a colorless, odorless and toxic gas at room temperature, it is necessary to pay minute attention when using it. For that reason, in the field of the synthetic chemistry using CO, the development of CO surrogate reagents as well as the study of novel synthetic reactions has proceeded. O

Cl

Materials Chemistry

H

Cl

O2 S

O

work as CO surrogate

N

O

CO

H

Cl 2,4,6-Trichlorophenyl Formate

N-Formylsaccharin

T3121

F0854

Manabe . have investigated novel CO surrogate agents focused on formic acid derivatives and found that 2,4,6-trichlorophenyl formate can act functionally as a CO equivalent.1) This compound is a stable crystalline solid at room temperature and it rapidly decomposes into CO and 2,4,6-trichlorophenol by treatment with a trialkylamine. generated CO is successfully applied to the palladium-catalyzed carbonylation of aryl/alkenyl halides and triflates to give their 2,4,6-trichlorophenol esters. Continuously, the given esters can be transformed into the corresponding carboxylic acid derivatives by the reaction with various nucleophiles. This carbonylation reaction is a highly practical synthetic method since it does not decrease the reaction yields even in gram-scale reactions.2)

O H

Cl

Cl +

O Cl T3121

R1 X

Pd(OAc)2 [A1424] Xantphos [B2709] NR3, solvent

O O 1

R

Cl

Cl Nucleophiles

O

O

R1

O Cl

R1 : aryl, alkenyl X : I, Br, OTf

OR2

R1

NR2

R1

SR2

2

Subsequently, Manabe . have developed the reductive carbonylation using -formylsaccharin as a CO equivalent.3) In this reaction, palladium acetate is used as a catalyst and the reaductive carbonylation of aryl bromides is accomplished in combination with triethylsilane as a nucleophile. The hydrogen atom on a formyl group of formed aldehydes is introduced by the addition of the hydride species from triethylsilane. R

Br

Br

O2 S

O N

+ N S

DMF, 75-85 oC

H Br

O

R Pd(OAc)2 [A1424] DPPB [B1246] Et3SiH [T0662] Na2CO3

F0854 Hydrogenation of hydride species from Ei3SiH

H O H N S

O H

In a case using 2,4,6-trichlorophenyl formate together with other nucleophiles, the carbonylation reaction tends to be complicated because of the nucleophilicity of 2,4,6-trichlorophenol formed as a byproduct. However, in the carbonylation reaction using -formylsaccharin, hydrosilanes can be directly used as a nucleophile because the nucleophilicity of formed saccharin is sufficiently inert. Product No.

Product Name

T3121 F0854

2,4,6-Trichlorophenyl Formate N-Formylsaccharin

Unit Size

1g 5g

References 1) T. Ueda, H. Konishi, K. Manabe, 2) H. Konishi, T. Ueda, K. Manabe, 3) T. Ueda, H. Konishi, K. Manabe,

2

. 2012, , 5370. . 2014, , 39. . 2013,

, 8611.

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

5g 25g

Oxidation

Synthetic Organic Chemistry

Oxidation

B2134

B1375

Materials Chemistry

Oxidation, making its target substance lose electrons, is one of the most basic reactions in organic chemistry and is exemplified by the combination with oxygen or a dehydrogenation reaction. In particular, it is often used for the transformation of alcohols to the corresponding aldehydes, ketones or carboxylic acids. Heavy metal compounds, such as chromium (VI) oxide and potassium permanganate, have been exploited for many years. Especially, chromium (VI) oxide has been utilized abundantly, based on the report of the control of oxidization powers by Jones or Sarett.1) Furthermore, chromium (VI) oxide have been improved as the Collins reagent2), PCC3) and PDC4) and are used in many fields. On the other hand, the Dess-Martin periodinane5), the Mukaiyama oxidizing agent6) and oxoammonium salts have been developed without containing harmful metals. Moreover, oxidation reactions employing inexpensive sodium hypochlorite or molecular oxygen have also been reported in the presence of oxidation catalysts such as tetrapropylammonium perruthenate (TPAP)7) and TEMPO8). This section shows the typical oxidizers and the catalysts used for oxidation reactions.

B1123

O Se

OH

C1944

CH3O

P1742

O0414

O CH3 C O

4

Pb

P0930

KMnO4

Fe3O4

N

C O

Bu

2

H N

O Si C18H37 O OCH 3

O

CH3 O O Os OH O OH CH3

Cr2O72 2

Cr2O7 2

N Bu 2

P1910

12MoO3 . H3PO4

OsO4

P1088

N H

. xH2O

Q0058

N H

FCrO3

Cr2O72-

N H

2

T1559 Bu

Ag2

O OCH3 O Si

ClCrO3

T1803

O

Bu

OCH3

O0308

P0931

N H

S0815

Se

Bu

L0021

H3C CH3 H3C CH3 N NO N Ru O C(CH3)3 (CH3)3C O Cl C(CH3)3 (CH3)3C

Bu

O

Metal Oxidants

N Bu Bu

Pr ReO4

Pr

N Pr

RuO4

Pr

Product No.

Product Name

B2134 B1375 B1123 C1944

Benzeneseleninic Acid Bis(4-methoxyphenyl) Selenoxide Bis(tetrabutylammonium) Dichromate Chloronitrosyl[N,N '-bis(3,5-di-tert-butylsalicylidene)-1,1,2,2-tetramethylethylenediaminato]ruthenium(IV)

Unit Size 1g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

5g 5g 10g 100mg

3

Synthetic Organic Chemistry

Oxidation

Product No.

Product Name

L0021 O0414 O0308 P1910 P1742 P0930 P0931 P1088 Q0058 S0815 T1803 T1559

Lead Tetraacetate (contains Acetic Acid) Osmium Catalyst supported on Magnetite (0.07-0.09mmol/g) Osmium Tetroxide (4% in Water) Phosphomolybdic Acid Hydrate Potassium Permanganate Pyridinium Chlorochromate Pyridinium Dichromate Pyridinium Fluorochromate Quinolinium Dichromate Silver(II) Pyridine-2-carboxylate Tetrabutylammonium Perrhenate Tetrapropylammonium Perruthenate

Unit Size

Materials Chemistry

B2897

25g

500g 1g 10mL 100g 300g 500g 500g 5g 25g 5g 5g 5g

25g 25g 25g

100g 100g 10g 1g 1g 1g

D3428

D3429

CH3

CH3

CH3

CH3

Perchlorates N

N ClO4

CH3

M1774

M2072

M1775

T0836

ClO4

CH3

T0839

CH3

CH3

ClO4 CH3

N

ClO4

CH3

CH3

CH3

N CH3

CH3 ClO4

CH2CH3

Bu

CH3

Bu

CH3

CH3CH2 N CH2CH3 ClO4

ClO4

CH2CH3

Bu

N

N CH3

N Bu

ClO4

CH3

T0841 CH3 CH3 N CH3

ClO4

CH3

Product No.

Product Name

B2897 D3428 D3429 M1774 M2072 M1775 T0836 T0839 T0841

9-(2-Biphenylyl)-10-methylacridinium Perchlorate 9-(2,5-Dimethylphenyl)-10-methylacridinium Perchlorate 9-(2,6-Dimethylphenyl)-10-methylacridinium Perchlorate 9-Mesityl-10-methylacridinium Perchlorate 9-Mesityl-2,7,10-trimethylacridinium Perchlorate 10-Methyl-9-phenylacridinium Perchlorate Tetrabutylammonium Perchlorate Tetraethylammonium Perchlorate Tetramethylammonium Perchlorate

Unit Size

B3152

4

25g

B3497

O

Organic Peroxides

1g 1g 1g 1g

B3153 CH3

O

C O O C

CH3

1g 100g

5g 5g 5g 5g 1g 5g 500g 25g 25g

Si CH3

CH3

CH3 O O Si CH3

CH3

CH3 C OOH CH3

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

Oxidation

C0357

C2223

D3411

M0927

Synthetic Organic Chemistry

O

O

CH3

CH3

C OOH

CH3

C O Mg2+

CH3 C O O C CH3

C OOH

CH3

CH3

CH3

. 6H2O

C OOH

Cl

O

2

Product No.

Product Name

B3152 B3497 B3153 C0357 C2223 D3411 M0927

Benzoyl Peroxide (wetted with ca. 25% Water) Bis(trimethylsilyl) Peroxide (contains Hexamethyldisiloxane) (ca. 30% in Hexane) tert-Butyl Hydroperoxide (70% in Water) 3-Chloroperoxybenzoic Acid (contains ca. 30% Water) Cumene Hydroperoxide (contains ca. 20% Aromatic Hydrocarbon) Di-tert-butyl Peroxide Monoperoxyphthalic Acid Magnesium Salt Hexahydrate

Unit Size 25g 5g 100g 25g 250g 100g 100mL 25g 500g

Materials Chemistry

A2678

B2539

B1175

O CH3

C O

I

Hypervalent Iodine Compounds

O

O

O

CF3 N

O

I

C O

I

O C CF3

I

O C CH3

BF4

N

Br

B1616

B2121 O

O CF3

C O

I

O C CF3

F

F

F

I0330

D4477 D2045 CH3

CH3 C OO

I

O

AcO OAc AcO I O

O

CH3

O

I0479 O

O

CH3 C O

I

O C CH3

O

CH3 C O

CH3

CH3

O

F CH3

F

I0072

I0073 I

O

n

I0791 HO

I

P1015

P1415

O

O

HO O

I

O

O

O

HO

I

O S

O

O

O C CH3

CH3 P

I O C CH3 O

Product No.

Product Name

A2678 B2539 B1175 B1616 B2121 D4477 D2045 I0330 I0479 I0072 I0073 I0791 P1015 P1415

1-Acetoxy-5-bromo-1,2-benziodoxol-3(1H)-one (ABBX) Barluenga's Reagent [Bis(trifluoroacetoxy)iodo]benzene (PIFA) [Bis(trifluoroacetoxy)iodo]pentafluorobenzene 1-(tert-Butylperoxy)-1,2-benziodoxol-3(1H)-one Dess-Martin Periodinane (8-12% in Dichloromethane) Dess-Martin Periodinane Iodobenzene Diacetate (PIDA) Iodomesitylene Diacetate Iodosobenzene 2-Iodosobenzoic Acid 2-Iodoxybenzoic Acid (IBX) (stabilized with Benzoic Acid + Isophthalic Acid) Koser Reagent Poly[4-(diacetoxyiodo)styrene] (PSDIB)

Unit Size 5g 1g

1g 10g

25mL 5g 25g 5g

5g 5g 1g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

1g 1g 25g 5g 1g 250mL 25g 250g 25g 5g 10g 25g 25g 5g

5

Oxidation

Synthetic Organic Chemistry

D3219

D3220

L0069 N(CH3)2

-Oxides

Cl

N

Cl

N

O

P0557

M0981 M2192

N

CH3

O

O

T1362 T0466

CH3 O

CH3

N

CH3

N O

Materials Chemistry

CH3

. xH2O

N CH3 O

O

Product No.

Product Name

D3219 D3220 L0069 M0981 M2192 P0557 T1362 T0466

2,6-Dichloropyridine N-Oxide 4-(Dimethylamino)pyridine N-Oxide Hydrate 2,6-Lutidine N-Oxide 4-Methylmorpholine N-Oxide (50% in Water, ca. 4.8mol/L) 4-Methylmorpholine N-Oxide Pyridine N-Oxide Trimethylamine N-Oxide Anhydrous Trimethylamine N-Oxide Dihydrate

Unit Size

A1348

1g 25mL 5g 25g 1g 25g

H0878

I0908

O

O

TEMPOs

CH3 CH3

N

O

O

O

O

CH3

CH3

CH3

CH3

O

M1197

O

O C

HN C CH3

5g 5g 25g 500mL 25g 500g 5g 500g

CH3 N

CH3

CH3

CH3 N

CH3

O

CH3

I

O

T1560 OCH3

CH3 CH3

CH3 N

CH3

CH3 CH3

O

CH3 N

CH3

O

Product No.

Product Name

A1348 H0878 I0908 M1197 T1560

4-Acetamido-TEMPO Free Radical 4-Benzoyloxy-TEMPO Free Radical 4-[2-[2-(4-Iodophenoxy)ethoxy]carbonyl]benzoyloxy-2,2,6,6-tetramethylpiperidin-1-oxyl 4-Methoxy-TEMPO Free Radical TEMPO Free Radical

Unit Size

T1837

T2507

Bi Cl

6

25g 5g 100mg 1g 5g 5g 25g T1956

CH3

Cl

Organic Bismuth Compounds

5g 1g

CH3O Cl BF4

Bi CH3

Bi Cl OCH3

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

OCH3

Oxidation

T2038

T1957

CF3

Synthetic Organic Chemistry

CF3

CH3 Cl

Cl Bi

CH3

Bi

Cl

Cl CH3

CF3

Product No.

Product Name

T1837 T2507 T1956 T2038 T1957

Triphenylbismuth Dichloride Triphenyl-2,6-xylylbismuthonium Tetrafluoroborate Tris(2-methoxyphenyl)bismuth Dichloride Tris(4-trifluoromethylphenyl)bismuth Dichloride Tri-o-tolylbismuth Dichloride

Unit Size 5g 1g 5g 1g 5g

100mg 1g 1g C1806

B2151

Materials Chemistry

A2065 O NH C CH3

Others

CH3

CH3 CH3

N

B0656

Bu

B2188

O Br

N

Br

CH3

NH C CH3

S

Cl

H3C

S N C CH3

CH3

O

2

H0362

CH3 Br

S 2O 8 2

N Bu

BF4

B2240

O Br

Bu

CH3

O

T0617

Bu

(NH4)2Ce(NO3)6

H3C C O Cl

CH3

H3C

Br

O

C1326 CH3

C1327

S O O

D0318

T0061

T0970

Cl

CH3

O

SO2NNa

Cl

O Cl

Cl

Cl

Cl

O

N

N O

C0076 CH3

CH3

O S O O

H1404

Cl

. 3H2O

CH3

I0074

O

Cl Cl

M2274

M2321

Cl

SO3

O

SO2NCl N

OH O

N

O

I

N CH3

CH3

O0310

P0998

2KHSO5 . KHSO4. K2SO4

S

N

.

CH3

N

CH3

SO3

(CH2)6SCH3

N CH3

CH3

T1559

. SO3 N

Pr Pr

N Pr

RuO4

Pr

Product No.

Product Name

A2065 C1806 B2151 T0617 B0656 B2240

4-Acetamido-2,2,6,6-tetramethyl-1-oxopiperidinium Tetrafluoroborate Ammonium Cerium(IV) Nitrate Bis(tetrabutylammonium) Peroxydisulfate Bromanil N-Bromosuccinimide N-tert-Butylbenzenesulfenamide

Unit Size

25g 1g

50g 5g 5g 100g 5g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

5g 500g 25g 25g 500g 25g

7

Synthetic Organic Chemistry

Oxidation

Product No.

Product Name

B2188 H0362 C1326 C1327 C0076 T0061 T0970 D0318 H1404 I0074 M2274 M2321 O0310 P0998 T1559

N-tert-Butylbenzenesulfinimidoyl Chloride tert-Butyl Hypochlorite (2R,8aS)-(+)-(Camphorylsulfonyl)oxaziridine [Asymmetric Oxidizing Reagent] (2S,8aR)-(-)-(Camphorylsulfonyl)oxaziridine [Asymmetric Oxidizing Reagent] Chloramine T Trihydrate Chloranil o-Chloranil Dichloramine T 2-Hydroxy-2-azaadamantane N-Iodosuccinimide 1-Methyl-3-[6-(methylsulfinyl)hexyl]imidazolium p-Toluenesulfonate 1-Methyl-3-[6-(methylthio)hexyl]imidazolium p-Toluenesulfonate Potassium Peroxymonosulfate [>45%(T) as KHSO5] Pyridine - Sulfur Trioxide Complex Tetrapropylammonium Perruthenate

Unit Size

200mg 5g

25g

1g 25g 1g 1g 25g 25g 5g 25g 1g 25g 1g 1g 25g 100g 1g

5g 500g 5g 5g 500g 500g 25g 500g 5g 100g 5g 5g 500g 500g 5g

Materials Chemistry

Many oxidizing agents may cause combustion or explosion upon mixture with flammable materials or upon exposure to heat, shock, and friction etc. Sufficient safety measures, such as using safety shields, wearing protective equipment, and using extreme caution should be taken when working with these reagents as well as disposing of the reagents.

References 1) K. Bowden, I. M. Heilbron, E. R. H. Jones, . 1946, 39; Review: S. V. Ley, A. Madin, 1991, , 253. 2) J. C. Collins, W. W. Hess, F. J. Frank, . 1968, , 3363. 3) E. J. Corey, J. W. Suggs, . 1975, , 2647. 4) E. J. Corey, G. Schmidt, . 1979, , 399. 5) D. B. Dess, J. C. Martin, . 1983, , 4155; R. E. Irekand, L. Liu, . 1993, , 2899. 6) J. Matsuo, D. Iida, K. Tatani, T. Mukaiyama, . 2002, , 223. 7) W. P. Griffith, S. V. Ley, G. P. Whitcombe, A. D. White, . 1987, 1625; Review: S. V. Ley, J. 1994, 639. Norman, W. P. Griffith, S. P. Marsden, 8) O. L. Lebelev, S. N. Kazarnovskii, . 1960, , 1631; Review: A. E. J. de Nooy, A. C. Besemer, H. van 1996, 1153. Bekkum,

8

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

Reduction

Synthetic Organic Chemistry

Reduction Reduction is a chemical reaction in which the target substances receive electrons, and is one of the most fundamental reactions in organic chemistry including the deoxygenation reaction and the hydrogenation reaction. The well-known reducing agents include metal hydrides such as LiAlH41) , boranes used in the hydride reduction, and hydrazine used in the Wolff-Kishner reduction.2) Sodium tris(1,1,1,3,3,3-hexafluoroisopropoxy)borohydride (1) is a selective reducing agent developed by Toshima . Aldehydes are selectively reduced in the presence of ketones and other reducible functions using 1 to afford the corresponding primary alcohols in high yields.3) OCH(CF3)2 H B OCH(CF3)2

Na

OCH(CF3)2

O

OTBS

CH3

O

1 / THF (3 eq.) CHO

Hexafluoroisopropanol, 25 °C, 1.5 h

Materials Chemistry

1 [S0810] OTBS OH

CH3 Y. 94%

In addition, the radical reductive reaction using silane compounds tris(trimethylsilyl)silane4) and tetraphenyldisilane (TPDS)5) as radical reducing agents has been developed avoiding the use of highly toxic tin compounds. This section shows the typical reducing agents. Table. Comparison of reactivities of hydride reducing agents for carbonyl compounds and imines Reagents

NaBH(OCOCH3)3 S0394

Reactions

Reactivity :

High

THF・BH3 T2346

NaBH3CN S0396

Middle

NaBH4 S0480

LiBH4 L0186

LiAlH4 L0170, L0203

Me2S・BH3 D1843 PhNEt2・BH3 D2581

Low

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

9

Reduction

Synthetic Organic Chemistry

D2972 D2971

Aluminum Hydrides

Metal Hydrides

L0159

L0203 L0170

LiAlH4

[(CH3)2CHCH2]2AlH

S0467 OC(CH3)3

Li

H Al

OC(CH3)3

NaAl(OCH2CH2OCH3)2H2

Materials Chemistry

OC(CH3)3

Product No.

Product Name

D2972 D2971 L0203 L0170 L0159 S0467

Diisobutylaluminum Hydride (17% in Toluene, ca. 1.0mol/L) Diisobutylaluminum Hydride (19% in Hexane, ca. 1.0mol/L) Lithium Aluminum Hydride (Powder) Lithium Aluminum Hydride (10% in Tetrahydrofuran, ca. 2.5mol/L) Lithium Tri-tert-butoxyaluminum Hydride (ca. 30% in Tetrahydrofuran, ca. 1.0mol/L) Sodium Bis(2-methoxyethoxy)aluminum Dihydride (70% in Toluene, ca. 3.6mol/L)

Unit Size 100mL 500mL 100mL 500mL 25g 100g 100mL 100mL 25g 100g 500g

T1473 (CH2)3CH3

Tin Hydrides

CH3(CH2)3 Sn H (CH2)3CH3

Product No.

Product Name

T1473

Tributyltin Hydride (stabilized with BHT)

Unit Size

S0481

Other Metal Hydrides

10

25g

250g

Z0010

NaH

H

Zr

Product No.

Product Name

S0481 Z0010

Sodium Hydride (60%, dispersion in Paraffin Liquid) Zirconocene Chloride Hydride

Cl

Unit Size 1g

100g 5g

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

500g 25g

Reduction

B1139

L0186

Ph3P

P1719

P1681

Cu

Synthetic Organic Chemistry

Ph3P

Borohydrides

L0164

CH(CH3)CH2CH3

. BH4

LiBH4

Li

H B CH(CH3)CH2CH3 CH(CH3)CH2CH3

P1380

S0480

S0396

CH3 CH2 N CH3

P

CH3

KBH4

CH3

CH3CH2CH

3

BH

NaBH4

K

NaBH3CN

BH3CN

S0810 OCH(CF3)2

OAc Na

T0917

Na

OCH(CF3)2

OAc

Bu

N Bu

T1553 CH3

CH3

Bu

H B OCH(CF3)2

AcO B H

T0852

CH3 N CH3

BH4

BH4

CH3

Product No.

Product Name

B1139 L0186 L0164 P1719

Bis(triphenylphosphine)copper Tetrahydroborate Lithium Borohydride (ca. 3mol/L in Tetrahydrofuran) Lithium Tri-sec-butylborohydride (ca. 21% in Tetrahydrofuran, ca. 1.0mol/L) (Polystyrylmethyl)trimethylammonium Cyanoborohydride cross-linked with 10% DVB (30-50mesh)

P1681 P1380 S0480 S0396 S0394 S0810 T0917 T0852 T1553

Potassium Borohydride Potassium Tri-sec-butylborohydride (ca. 1.0mol/L in Tetrahydrofuran) Sodium Borohydride Sodium Cyanoborohydride Sodium Triacetoxyborohydride Sodium Tris(1,1,1,3,3,3-hexafluoroisopropoxy)borohydride Tetrabutylammonium Borohydride Tetramethylammonium Borohydride Tetramethylammonium Triacetoxyborohydride

OAc

Unit Size

B1827

Borane Complexes

Boranes

5g 100mL 100mL

5g 25g 25g 100g Price on request 25g 100g 500g 5g 25g 250g 25g 100g 5g 5g 25g 5g 25g 5g 25g

(2.6-3.0mmol/g)

D2581

OAc

CH3 N CH3 AcO B H

CH3

Bu

Materials Chemistry

S0394

T2346

CH3

CH3

CH3 C S(CH2)2S CH3

. 2BH3

.

C CH3 CH3

BH3

O

D1843 CH2CH3 N

.

BH3

CH3SCH3

. BH3

CH2CH3

Product No.

Product Name

B1827 T2346

1,2-Bis(tert-butylthio)ethane Borane Borane - Tetrahydrofuran Complex (8.5% in Tetrahydrofuran, ca. 0.9mol/L)

D2581 D1843

(stabilized with Sodium Borohydride)

N,N-Diethylaniline Borane Dimethyl Sulfide Borane

Unit Size 1g 100mL 500mL 25g 100g 25mL 100mL

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

11

Reduction

Synthetic Organic Chemistry

B1264

Borane-Amine Complexes

B1569

CH3 CH3 C NH2

. BH3

CH3

N

B3018

CH3CH2

. BH3

CH3

CH3

. BH3

CH3CH2 N

CH3 N

Product Name

B1264 B4084 B3018 M0898 B1569 D1842 T1180 T1181

Borane - tert-Butylamine Complex Borane - 5-Ethyl-2-methylpyridine Complex Borane - 2-Methylpyridine Complex Borane - Morpholine Complex Borane - Pyridine Complex Dimethylamine Borane Triethylamine Borane Trimethylamine Borane

I0796

CH3

B Cl CH3

CH3

I0797

CH3 B Cl

H2 B

CH3 CH3 B H2

CH3

CH3 CH3 CH3

CH3

H2 B

N

CH3 CH3

CH3

CH3 CH3

CH3 CH3 N

B H2

CH3

CH3

2

Product Name

C1614 C2023 C1615 I0796 I0797

(+)-B-Chlorodiisopinocampheylborane (58% in Hexane, ca. 1.6mol/L) (-)-B-Chlorodiisopinocampheylborane (55-65% in Heptane, ca. 1.7mol/L) (-)-B-Chlorodiisopinocampheylborane (60% in Hexane, ca. 1.7mol/L) (+)-Isopinocampheylborane TMEDA Complex (-)-Isopinocampheylborane TMEDA Complex

Unit Size

C1492

100mL 100mL 100mL 5g 5g

C0778

D2403

CH(CH3)2

Silanes

Cl

CH(CH3)2

D1825

D2406 D2820

SiH2

Si H

Si CH3

CH3

Si H OCH2CH3

CH3

P1291 H

OCH2CH3

CH3

H Si Cl

CH3

12

N

N

CH3 CH3

CH3

CH3

2

CH3

Product No.

CH3

. BH3

25g 100g 25mL 100mL 5g 25g 5g 25g 25mL 25g 500g 25g 25g

C2023 C1615 CH3

Si H

O

Unit Size

C1614

D2196

. BH3

CH3

CH2CH3

Product No.

Other Boranes

N

T1181 CH2CH3

CH3

H N

. BH3

CH3

T1180

H N

M0898

. BH3 N

CH3

D1842

. BH3

Materials Chemistry

B4084

T1437 SiH3

CH3 CH3

CH3

Si

O Si

H

H

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

CH3

Reduction

T1896

T0398

T0662

T1334

Si

Si

H

H

Cl

CH3CH2 Si H CH2CH3

Cl

T0661

i

(CH2)5CH3 iPr

CH3(CH2)5 Si H (CH2)5CH3

Synthetic Organic Chemistry

CH2CH3

Cl H Si

T1533 Pr

Si

H

iPr

T1463 Si(CH3)3 Si

H

(CH3)3Si

Si H Si(CH3)3

Product Name

C1492 C0778 D2403 D2196 D2406 D2820 D1825 P1291 T1437 T1896 T0398 T0662 T1334 T1533 T0661 T1463

Chlorodiisopropylsilane Chlorodimethylsilane Diethoxymethylsilane [Hydrosilylating Reagent] Dimethylphenylsilane Diphenylsilane Diphenylsilane Methyldiphenylsilane Phenylsilane 1,1,3,3-Tetramethyldisiloxane 1,1,2,2-Tetraphenyldisilane Trichlorosilane Triethylsilane Trihexylsilane Triisopropylsilane Triphenylsilane Tris(trimethylsilyl)silane (stabilized with TBBP)

Materials Chemistry

Product No.

Unit Size

5g

5mL

C2648

H0697 H0204 H0172

O

5mL 25mL 25mL 250mL 25mL 25mL 5g 25g 5g 25g 25mL 5mL 25mL 25mL 250mL 1g 5g 25g 500g 25mL 250mL 10g 25mL 100mL 25g 5mL 25mL

H0169

C NHNH2

Hydrazines, Hydrazides

H2NNH2

H2NNH2

. 2HBr . xH2O

Cl

H0170

H0173

H0174

I0777 SO2NH N C

H2NNH2

. 2HCl

H2NNH2 . HBr

Product No.

Product Name

C2648 H0697 H0204 H0172 H0169 H0170

3-Chlorobenzohydrazide Hydrazine Anhydrous Hydrazine Monohydrate (79%) Hydrazine Monohydrate Hydrazine Dihydrobromide Hydrate Hydrazine Dihydrochloride

H2NNH2

. HCl

NO2

CH3 CH3

Unit Size 5g 25g 10g 100g 25g 500g 25mL 500mL 25g 500g 25g 500g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

13

Synthetic Organic Chemistry

Reduction

Product No.

Product Name

H0173 H0174 I0777

Hydrazine Monohydrobromide Hydrazine Monohydrochloride N '-Isopropylidene-2-nitrobenzenesulfonohydrazide

Unit Size 25g 25g

D4311

D3775 O

Others

CH3

Materials Chemistry

S0494

T0430

OC(CH3)3 N H

H1221 O

O

O

(CH3)3CO

CH3CH2O C CH3

CH3

T0488

500g 500g 5g

C OCH2CH3 N H

HI

CH3

T0519

T1819

CH3

SmI2

OCH3

O CH3

O

P

O

CH3

CH3O

P

OCH3

Product No.

Product Name

D4311 D3775 H1221 S0494 T0430 T0488 T0519 T1819

Di-tert-butyl 1,4-Dihydro-2,6-dimethyl-3,5-pyridinedicarboxylate Diethyl 1,4-Dihydro-2,6-dimethyl-3,5-pyridinedicarboxylate Hydriodic Acid (57%) Samarium(II) Iodide (ca. 0.1mol/L in Tetrahydrofuran) Triethyl Phosphite Trimethyl Phosphite Triphenylphosphine Triphenylphosphine Selenide

P

P

Se

Unit Size 1g

1g 5g

5g 25g 300mL 25mL 25mL 500mL 25mL 25g 500g 5g

Many reducing agents may spontaneously ignite on contact with air, or may react violently with water to produce flammable gases. Sufficient safety measures, such as using safety shields, wearing protective equipment, and using extreme caution should be taken when working with these reagents as well as disposing of the reagents.

Hydrogenation Catalysts Product No.

Product Name

P1785 P1491 P1701 P1702 P1703 P1490 P1528 P1786 P1720 P1944 R0075 R0076 S0487

Palladium 10% on Carbon (wetted with ca. 55% Water) Palladium 10% on Carbon (wetted with ca. 55% Water) Palladium 5% on Barium Carbonate Palladium 5% on Barium Sulfate Palladium 5% on Calcium Carbonate (poisoned with Lead) Palladium 5% on Carbon (wetted with ca. 55% Water) Palladium Hydroxide 20% on Carbon (wetted with ca. 50% Water) Palladium on SH Silica Gel (0.1mmol/g) Platinum(IV) Oxide Poly(methylphenyl)silane supported Palladium/Alumina Hybrid Catalyst [=Pd / (PSi-Al2O3)] Rhodium 5% on Carbon (wetted with ca. 55% Water) Ruthenium 5% on Carbon (wetted with ca. 50% Water) Skeletal Nickel Catalyst slurry in Water

Unit Size 5g 5g 5g 5g 5g 10g

5g

25g 25g 10g 25g 25g 25g 50g 1g 200mg 1g 1g 25g 50g

R0129 O

Asymmetric Hydrogenation Catalysts

Ruthenium Complex Catalysts for Asymmetric Hydrogenation of Ketones

O O O

Ar2 Cl P Ru P Ar2 Cl

H2 N

Me OMe

N H2

Me OMe

Ar= Me

14

Me

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

Reduction

R0128

R0131 Ar2 Cl P Ru P Ar2 Cl

O O O

Me

H2 N

R0130

O

Me

O OMe

N H2

O

Ar2 Cl H2 P N Ru N P Ar2 Cl H2

O O

O O O

Me

Me OMe

Ar=

Ar=

R0133

Me

Me

R0134 Ar2 Cl H2 P N Ru N P Ar2 Cl H2

Me

Me

Ar=

H2 H N H2 N

Me

OMe Ar2 Cl H2 P N Ru H2 N P Ar2

Me

OMe

H Me Me

MeO

Ar=

Me

Me

Ar=

Me

Product Name

R0129 R0128 R0131 R0130 R0133 R0132 R0135 R0134 R0139 R0138

RuCl2[(R)-dm-segphos®][(R)-daipen] RuCl2[(S)-dm-segphos®][(S)-daipen] RuCl2[(R)-dm-segphos®][(R,R)-dpen] RuCl2[(S)-dm-segphos®][(S,S)-dpen] RuCl2[(R)-xylbinap][(R)-daipen] RuCl2[(S)-xylbinap][(S)-daipen] RuCl2[(R)-xylbinap][(R,R)-dpen] RuCl2[(S)-xylbinap][(S,S)-dpen] (R)-RUCY®-XylBINAP (S)-RUCY®-XylBINAP

Me

Materials Chemistry

Product No.

OMe

Ar=

Me

Me MeO

Me

OMe

R0138 Ar2 Cl P Ru P Ar2

Ar=

Me

Me OMe

Me

R0139

Ar2 Cl H2 P N Ru N P Ar2 Cl H2

OMe

N H2

Me

Ar2 Cl H2 P N Ru N P Ar2 Cl H2

Me

Ar=

Me

R0135

Me

H2 N

Me

Ar=

Me

R0132 Ar2 Cl P Ru P Ar2 Cl

Ar2 Cl H2 P N Ru N P Ar2 Cl H2

Synthetic Organic Chemistry

O

Unit Size 200mg 200mg 200mg 200mg 200mg 200mg 200mg 200mg 200mg 200mg

R0146

R0147 Me

Ruthenium Complex Catalysts for Asymmetric Hydrogenation of Olefins and Functionalized Ketones

Ru P Ar2

R0156 Me

Ar2 P Cl

O

Ar2 P

Cl

Me

O Ru Cl

P Ar2

Me

1g 1g 1g 1g 1g 1g 1g 1g 1g 1g

Cl

Me Me

O O

Me Ar2 P Ru Cl P Ar2 Me

Me

Cl

Me Ar=

Ar=

Ar=

Me

R0157

R0158 Me Ar2 P Ru Cl P Ar2 Me

O O O O

O

Me

O

Cl

O

Me

O

R0159 Me Ar2 P Ru Cl P Ar2 Me

O Me

O

Cl

O

Ar=

Ar=

Cl

Me

Ar2 P

Cl

Ru P Ar2

Me

Ar=

Me

O tBu

Cl

Me

Cl

O

Ar2 P Ru P Ar2

Cl

Me

Me

Cl

Ar=

Product Name

R0146 R0147 R0156 R0157 R0158 R0159

[RuCl(p-cymene)((R)-binap)]Cl [RuCl(p-cymene)((S)-binap)]Cl [RuCl(p-cymene)((R)-dm-segphos®)]Cl [RuCl(p-cymene)((S)-dm-segphos®)]Cl [RuCl(p-cymene)((R)-dtbm-segphos®)]Cl [RuCl(p-cymene)((S)-dtbm-segphos®)]Cl

O

Me Ar2 P Ru Cl

P Ar2

Me

Cl

Me

Ar=

Ar=

Me Ar2 P Ru Cl P Ar2 Me

Me

Cl

Me Ar=

Me

Product No.

O O

Me

Me Me

Cl

R0151 Me Ar2 P Ru Cl P Ar2 Me

Me

Ar=

O

R0155 Me

OMe

R0150 Me

Ru

O

Cl

tBu

R0149

P Ar2

Me

tBu

Me Ar2 P

O

Ar=

OMe

Me

R0148

O

tBu

R0154 Me Ar2 P Ru Cl P Ar2 Me

Me

Unit Size 200mg 200mg 200mg 200mg 200mg 200mg

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

1g 1g 1g 1g 1g 1g

15

Synthetic Organic Chemistry

Reduction

Product No.

Product Name

R0154 R0155 R0148 R0149 R0150 R0151

[RuCl(p-cymene)((R)-segphos®)]Cl [RuCl(p-cymene)((S)-segphos®)]Cl [RuCl(p-cymene)((R)-tolbinap)]Cl [RuCl(p-cymene)((S)-tolbinap)]Cl [RuCl(p-cymene)((R)-xylbinap)]Cl [RuCl(p-cymene)((S)-xylbinap)]Cl

Unit Size 200mg 200mg 200mg 200mg 200mg 200mg

R0123

R0122

Ruthenium Complex Catalysts for Asymmetric Transfer Hydrogenation of Ketones

Materials Chemistry

R0124

R0127 CH3

F

F

F

CH3 F O S O N Ru N H2

Cl

CH3

F

F

F

CH3 F O S O N Ru

CH3 CH3

R0126 CH3

R0125 F

F

N H2

N H2

CH3 Cl

CH3

CH3 O S O N Ru N H2

CH3

Cl

CH3

Cl CH3

Product No.

Product Name

R0123 R0122 R0125 R0124 R0127 R0126 T3078 T3077

RuCl[(R,R)-Fsdpen](p-cymene) RuCl[(S,S)-Fsdpen](p-cymene) RuCl[(R,R)-Tsdpen](p-cymene) RuCl[(S,S)-Tsdpen](p-cymene) RuCl[(R,R)-Tsdpen](mesitylene) RuCl[(S,S)-Tsdpen](mesitylene) (R,R)-Ts-DENEB® (S,S)-Ts-DENEB®

CH3 O S O N Ru N H2

CH3

CH3 Cl

N H2

T3078 S O

CH3 O N

Ru N

H

Cl

CH3 Cl H

Ru N

O O S N O

CH3

Cl CH3

Unit Size 200mg 200mg 200mg 200mg 200mg 200mg 200mg 200mg

*These products were merchandised under the technical tie-up with TAKASAGO INTERNATIONAL CORPORATION.  SEGPHOS®, RUCY®, and DENEB® are registered trademarks of TAKASAGO INTERNATIONAL CORPORATION.

References 1972, 217. 1) Review: J. Malek, M. Cerny, 2) Review: N. Kishner, . 1911, , 582; L. Wolff, . 1912, , 86; R. O. Hutchins, M. K. 1991, , 327. Hutchins, 2008, 3) Y. Kuroiwa, S. Matsumura, K. Toshima, , 2523. 4) C. Chatgilialoglu, D. Griller, M. Lesage, . 1988, , 3641. 5) O. Yamazaki, H. Togo, S. Matsubayashi. M. Yokoyama, . 1998, , 1921.

16

CH3

T3077 O

CH3 O S O N Ru

CH3 O S O N Ru

CH3

CH3

CH3

1g 1g 1g 1g 1g 1g

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

1g 1g 1g 1g 1g 1g 1g 1g

Halogenation

Synthetic Organic Chemistry

Halogenation Halogenation is a basic and fundamental transformation in organic chemistry, and halogenated compounds are of extreme importance as building blocks in organic synthesis. The development of modern coupling reactions, such as the Suzuki-Miyaura and Mizoroki-Heck reactions, have greatly increased the demand for halogenated compounds as starting materials. In response to this situation, many novel halogenating reagents have been developed. The page below shows some examples of brominating and iodinating reagents, which have been released recently in our lineup of products.

NO2

O

NO2 R O

1a)

Br

HN

Y. 88%

NH2 3a)

N N

O

Br

NHBr Y. 90-99%

Br N OH O

Br

DBI (1)

1b)

NO2

3b)

[D3753]

Y. 68%

O R

Br

N N

Materials Chemistry

Example of brominating products: Dibromoisocyanuric acid (DBI) (1), which was first reported by Gottardi, is a mild and highly effective brominating reagent,1,2) and has superior brominating ability when compared with -bromosuccinimide (NBS), which is frequently used in organic synthesis. For instance, nitrobenzene was converted to the 3-bromonitrobenzene in 88% yield with 1 in conc. sulfuric acid in 5 min at 20ºC, 1a) but in only 70% yield with NBS in 50% sulfuric acid in 3 h at 85ºC. Thus 1 has been widely used as an effective brominating reagent.3)

Y. 69%

Example of iodinating products: 1,3-Diiodo-5,5’ -dimethylhydantoin (DIH) (2), which was first reported by Ozazi, is an useful iodinating reagent.4) 2 has higher reactivity and selectivity than molecular iodine or -iodosuccinimide (NIS), which are frequently used for iodination reaction. 2 is a pale yellow solid that does not sublime like molecular iodine, and has low toxicity, which makes it easier to handle. In addition, dimethylhydantoin, which is formed after the reaction, can easily be removed by aqueous extraction. 2 reacts smoothly at room temperature with aromatic compounds in the presence of sulfuric acid to give the corresponding iodinated aromatic compounds in a high regioselectivity and a high yield. Moreover, even low-activated substances such as nitrobenzene can easily be iodinated by using sulfuric acid.5) I

O

N

CH3 CH3

N

O

I DIH (2) [D3657]

OMe

EtOH-conc.H2SO4, 20 °C, 10 min

NO2

OMe

2 (0.5 eq.)

Y. 97%

I

NO2

2 (1 eq.) 90% H2SO4, 0 °C, 60 min

Y. 75%

I COOH F

COOH

2 (1 eq.) 90% H2SO4, 0 °C, 90 min

Y. 75%

F I

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

17

Halogenation

Synthetic Organic Chemistry

B2440

B3664

D1868 SF3

CH3OCH2CH2

Fluorination

CH3OCH2CH2

CH3

F N S

CH3

F

Et

F

N S

F

Et

CH3 C CH3

F

F

CH3

D3812

F0335

F0358

F0344

F0225 SO3

O N

N

F

F

O

N

S N S O F O

N

Materials Chemistry

2BF4

Cl

N

CH2Cl

2BF4

F0343

F

F0327

Cl

BF4

N

F0346

F0328 CH3

F

CH3

F

CH3

H0598 CH3 Et

BF4

N

N

CH3

F

F

M1573

BF4

CF3SO3 N

CH3

CF3SO3 CH3

N

P1888

P0999

T1592

Ph

Si F Ph

T1635

F

F Ph Bu4N

Bu4N

Ph

Bu

N

O

T1909

Bu

. (HF)x

KHF2

KF

Ph

Sn F

Ph

N Bu

H2F3

Bu

HF2

T2027

Bu Bu

N Bu Bu

T1037 T1339 T1125 T1338

Bu Bu

F

T1295

SF3 N

CF3

F

F

F

P1758

Et

CH3

F

N

N Bu F

. xH2O

(CH3CH2)4NF

. 4HF

Bu

T2026

T2754

T2023

T2022

CH3 (CH3CH2)4NF

18

. 3HF

CH3

N CH3 CH3

F

. 4H2O

(CH3CH2)3N

. 5HF

(CH3CH2)3N

. 3HF

Product No.

Product Name

B2440 B3664 D1868 D3812 F0335 F0358 F0344 F0225 F0343 F0327 F0346 F0328 H0598 M1573

Bis(2-methoxyethyl)aminosulfur Trifluoride 4-tert-Butyl-2,6-dimethylphenylsulfur Trifluoride (FLUOLEADTM) (Diethylamino)sulfur Trifluoride (DAST) 1,1'-Difluoro-2,2'-bipyridinium Bis(tetrafluoroborate) N-Fluorobenzenesulfonimide (NFSI) N-Fluoro-N '-(chloromethyl)triethylenediamine Bis(tetrafluoroborate) (F-TEDA-BF4) 1-Fluoro-2,6-dichloropyridinium Tetrafluoroborate 2-Fluoro-1-methylpyridinium p-Toluenesulfonate 1-Fluoropyridinium Tetrafluoroborate 1-Fluoropyridinium Trifluoromethanesulfonate 1-Fluoro-2,4,6-trimethylpyridinium Tetrafluoroborate 1-Fluoro-2,4,6-trimethylpyridinium Trifluoromethanesulfonate Ishikawa's Reagent Morpholinosulfur Trifluoride (Morph-DAST)

Unit Size 5g 5g

5g

25g

25g 5g 25g 5g 5g 5g 5g 5g 100g 1g

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

25g 5g 100g 1g 25g 100g 25g 25g 25g 25g 5g 25g 500g 5g

Halogenation

Product Name

P1758 P1888 P0999 T1295 T1909 T1592 T1635 T1037 T1339 T1125 T1338 T2027 T2026 T2754 T2023 T2022

Potassium Fluoride Potassium Hydrogenfluoride Pyridinium Poly(hydrogenfluoride) Tetrabutylammonium Bifluoride Tetrabutylammonium Difluorotriphenylsilicate Tetrabutylammonium Difluorotriphenylstannate Tetrabutylammonium Dihydrogen Trifluoride Tetrabutylammonium Fluoride Hydrate Tetrabutylammonium Fluoride (70-75% in Water) Tetrabutylammonium Fluoride (ca. 1mol/L in Tetrahydrofuran) Tetrabutylammonium Fluoride (ca. 1mol/L in Tetrahydrofuran) Tetraethylammonium Fluoride Tetrahydrofluoride Tetraethylammonium Fluoride Trihydrofluoride Tetramethylammonium Fluoride Tetrahydrate Triethylamine Pentahydrofluoride Triethylamine Trihydrofluoride

Unit Size Synthetic Organic Chemistry

Product No.

300g 500g 100g 25g 25g 5g 25g 100g 500g 100mL 500mL 10g 10g 25g 10g 10g

25g 5g 5g 1g 5g 25g 25g 25mL 25mL 100mL

5g

Materials Chemistry

B1543

H0362

C0075

CH3 CH2

Chlorination

C0076

N CH3 CH3

C1374

C0202

Cl

SO2NCl

H3C H3C C O Cl

. xH2O

C0802

C0291

Cl

SO2NNa

O

O

SO2NNa ClCH2OCH3

CH3

C0460

N Cl

N Cl

. 3H2O

CH3

Na

H3C

ICl4

O

O

D0318

D1645

M0094

M0970

Cl SO2NCl

Cl N Cl

N

O

Cl

N

Cl

CH3

OCH3

O

S Cl

CH3OCH2

O

Cl

C Cl

CH3

O0082

D1003 O O

Cl Cl

Cl

O

O

N

T0620

T2048 T2040

O

O

Cl

O

NNa N

T0611

Cl

Cl

Product No.

Product Name

B1543 H0362 C0075 C0076 C1374 C0202

Benzyltrimethylammonium Tetrachloroiodate tert-Butyl Hypochlorite Chloramine B Hydrate Chloramine T Trihydrate o-Chloramine T Chloromethyl Methyl Ether

S

Cl

O

N

N N

O

Cl CCl3

S Cl O

O

Cl

Unit Size 25g 25g 25g 25g

100g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

5g 500g 500g 500g 25g 500g

19

Synthetic Organic Chemistry

Halogenation

Product No.

Product Name

C0802 C0291 C0460 D0318 D1645 M0094 M0970 O0082 D1003 T2048 T2040 T0620 T0611

N-Chlorophthalimide N-Chlorosuccinimide Cyanuric Chloride Dichloramine T Dichloromethyl Methyl Ether Methanesulfonyl Chloride Methoxyacetyl Chloride Oxalyl Chloride Sodium Dichloroisocyanurate Thionyl Chloride (ca. 1mol/L in Dichloromethane) Thionyl Chloride Trichloroisocyanuric Acid Trichloromethanesulfonyl Chloride

Unit Size

25g

Materials Chemistry

B2358

B2553

CH3 CH2

B0530

CH3

B2152

N H

Br

S O

N

CH3

D3976 N

Br

O

O

Br

N

Br

D1987

O

P1743

O

Br Br

O

D1787

O

Cl

CH3

C C Cl

Br3

Cl Cl

N H

O

P0825

T1235

T1284 O

N N H

N(CH3)2

Br Br

CH3

O NaN

Br

Br

. xH2O O

PBr3

N H

Bu

Br Bu

Br3

N Bu Br3 Bu

Br

Br

P0928 CH3 CH3 N CH3 Br3

20

. HBr3

N

O N

Br

B2148

N

Br3

(CH2)3CH3

D1710

HN

CH3

N

Cl

Br

N Br

Br

CH3

O

O

O

N

S

CH3

B3596

Br

D3753 O

O N CH3

Cl

Br

Br

CH3

Br

B

B1697

Cl

D1265

Br

CH3 CH3

O

O

CH3

NC

N Br

CH3 PF6

B3311

B0662

O

Br

N Br N

O

B0656

N

CH3

Br3

B1016

O

Br2

CH3 CH3

N CH3 CH3

B2414

500g 500g 500g 500g 250g 500g 500g 500g 500g 500mL 500mL 25g 500g 5g 25g

25g

T1382

Bromination

25g 100g 25g 25g 25g 25g 25g 100g 25g

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

Halogenation

Benzyltrimethylammonium Tribromide Bis(2,4,6-trimethylpyridine)bromonium Hexafluorophosphate Boron Tribromide (17% in Dichloromethane, ca. 1mol/L) Bromine N-Bromoacetamide 2-Bromo-2-cyano-N,N-dimethylacetamide Bromodimethylsulfonium Bromide N-Bromophthalimide N-Bromosaccharin N-Bromosuccinimide Bromotrichloromethane 1-Butyl-3-methylimidazolium Tribromide 1,8-Diazabicyclo[5.4.0]-7-undecene Hydrogen Tribromide 1,3-Dibromo-5,5-dimethylhydantoin Dibromoisocyanuric Acid 5,5-Dibromomeldrum's Acid (=5,5-Dibromo-2,2-dimethyl-4,6-dioxy-1,3-dioxane) 1,2-Dibromo-1,1,2,2-tetrachloroethane 4-Dimethylaminopyridinium Bromide Perbromide Monosodium Bromoisocyanurate Hydrate Phosphorus Tribromide Pyridinium Bromide Perbromide 2,4,4,6-Tetrabromo-2,5-cyclohexadienone Tetrabutylammonium Tribromide Trimethylphenylammonium Tribromide

Unit Size

B1604

5g 1g 90g 5g

25g

25g 5g 5g 5g

25g

B2539

CH2

CH3

D3657 O CH3

I0784

N N

I O

I0074 O S

I

N

H1221

BF4

CH3

I

O

I

CH3 I

N

CH3

PF6

CH3

I0604

T2717

O

. ICl

I N

I2

HI

CH3

P2086

N

N

CH3 CH3SCH N

I

O

N

CH3

D4340

CH3

ICH2CH2Cl

N

N CH3 ICl2 CH3

C1190

25g 5g 100g 25g

B2359

CH3

Iodination

5g 5g 5g 100g 25g

25g 5g 100mL 500g 25g 5g 25g 25g 25g 500g 500g 5g 5g 500g 25g 25g 25g 25g 25g 300g 500g 25g 500g 500g

Materials Chemistry

Product Name

T1382 B2358 B2553 B2414 B0530 B1016 B3311 B1697 B2152 B0656 B0662 B3596 D3976 D1265 D3753 D1710 D1987 D1787 B2148 P1743 P0825 T1235 T1284 P0928

Synthetic Organic Chemistry

Product No.

I0308 CH3

CH3

N CH3 ICl2 CH3

CH3 CH3

Si

I

CH3

O

Product No.

Product Name

B1604 B2539 B2359 C1190 D3657 D4340

Benzyltrimethylammonium Dichloroiodate Bis(pyridine)iodonium Tetrafluoroborate Bis(2,4,6-trimethylpyridine)iodonium Hexafluorophosphate 1-Chloro-2-iodoethane (stabilized with Copper chip) 1,3-Diiodo-5,5-dimethylhydantoin N,N-Dimethyl-N-(methylsulfanylmethylene)ammonium Iodide

Unit Size 5g 1g 1g 5g 5g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

25g 1g 5g 5g 25g 25g

21

Synthetic Organic Chemistry

Halogenation

Product No.

Product Name

H1221 I0604 I0784 I0074 P2086 T2717 I0308

Hydriodic Acid (57%) Iodine N-Iodosaccharin N-Iodosuccinimide Pyridine Iodine Monochloride Tetramethylammonium Dichloroiodate Trimethylsilyl Iodide (stabilized with Aluminum)

Unit Size 300mL 500g 5g 25g 100g 1g 5g 5g 5g 25g

25g 5g

References

Materials Chemistry

2002, 83. 1) a) W. Gottardi, . 1968, , 815; b) W. D. Brown, A. H. Gouliaev, 2) S. C. Virgil, in , ed. by L. A. Paquette, John Wiley & Sons, Chichester, 2001, pp. 1560-1561. 3) a) Z. P. Demko, M. Bartsch, K. B. Sharpless, . 2000, , 2221; b) T. R. Walters, W. W. Zajac Jr., J. M. Woods, . 1991, , 316. 4) O. O. Orazi, R. A. Corral, H. E. Bertorello, . 1965, , 1101. 5) V. K. Chaikovskii, V. D. Filimonov, A. A. Funk, V. I. Skorokhodov, V. D. Ogorodnikov, . 2007, , 1291.

22

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

Trifluoromethylation

Synthetic Organic Chemistry

Trifluoromethylation

O R1

R2

OH

cat. F

F3C SiMe3

+

R1

[T1570] CuI (10 mol%) phen (10 mol%)

I F3C SiEt3

+

X

KF, NMP/DMF

[T2764]

Materials Chemistry

The size of a fluorine atom is similar to a hydrogen atom but the electric property of it is more electronegative. So, by replacing a hydrogen atom of substances with a fluorine atom, their biological properties can be dramatically changed without a conformational change. Recently, the synthetic and biological studies of fluorinated molecules have attracted a lot of interest in the fields of pharmaceuticals and agrochemicals research. Especially, the synthetic study of the trifluoromethyl group-containing compounds is now actively proceeding. As a method for direct trifluoromethylation, nucleophilic and electrophilic/radical fluorinating reactions are commonly used. Ruppert-Prakash reagent ((Trifluoromethyl)trimethylsilane) is the most popular nucleophilic trifluoromethylating reagent and which readily reacts with a fluoride ion to release the trifluoromethylanion species. This active species shows nucleophilicity and reacts with carbonyl compounds to proceed with the trifluoromethylation.1) Also, the nucleophilic trifluoromethylation of aromatic halides can be performed with the use of copper catalysts.2)

R2 CF3 CF3

X

The study of electrophilic trifluoromethylations has lagged compared to that of nucleophilic trifluoromethylations. However, recently some reagents usable for electrophilic trifluoromethylation have been reported. Shibata . have developed an electrophilic α-trifluoromethylation of β-ketoesters using the fluorinated Johnson reagent 1.3) The hypervalent iodine(III)‒CF3 reagents 2 and 3 developed by Togni . are widely used for trifluoromethylations of thiols, alcohols, phosphines, and heteroarenes.4) Also, Baran . have reported the radical trifluoromethylation of heteroarenes using the Langlois reagent or zinc(II) bis(trifluoromethanesulfinate) (Zn(SO2R)2) with -butyl hydroperoxide.5) CF3

O

CF3

I

S N CF3

I O

BF4

O O

Shibata Reagent I

Togni Reagent

Togni Reagent II

2 [T2624]

3 [T3014]

1 [O0367]

F0311

O0367 O

F

P2172 O

O

S CF2 C OCH3

S N

O

CF3

T2764

CH3 CH3

T3014 CH2CH3

CH3CH2 Si CF3 CH2CH3

CF3

N BF4

Cu N

CF3

O O

Langlois Reagent [T2033]

O

O

CF3 PPh3

CH3 CH3

Baran Reagent

T2033

CF3

CF3SO2Na

ONa

T1570 I

Zn(SO2CF3)2

[Z0028]

T1336

T2624 I

CF3SO2Na

T2883 CH3 CH3 Si CF3

P

Cu CF3

CH3 3

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

23

Trifluoromethylation

Synthetic Organic Chemistry

Z0028 O CF3

Zn2

S O

2

Materials Chemistry

. 2H2O

Product No.

Product Name

F0311 O0367 P2172 T1336 T2033 T2764 T3014 T2624 T1570 T2883 Z0028

Methyl Difluoro(fluorosulfonyl)acetate [(Oxido)phenyl(trifluoromethyl)-λ4-sulfanylidene]dimethylammonium Tetrafluoroborate (1,10-Phenanthroline)(trifluoromethyl)(triphenylphosphine)copper(I) Sodium Trifluoroacetate Sodium Trifluoromethanesulfinate Triethyl(trifluoromethyl)silane 1-Trifluoromethyl-1,2-benziodoxol-3(1H)-one (contains 60% Diatomaceous earth) 1-Trifluoromethyl-3,3-dimethyl-1,2-benziodoxole (Trifluoromethyl)trimethylsilane (Trifluoromethyl)tris(triphenylphosphine)copper(I) Zinc(II) Bis(trifluoromethanesulfinate) Dihydrate

Unit Size 5g 200mg 1g 25g 100g 5g 1g 1g 1g 5g 1g 1g

25g 1g 5g 500g 25g 5g 5g 5g 25g 5g 5g

References 1) a) I. Ruppert, K. Schlich, W. Volbach, . 1984, , 2195. b) G. K. S. Prakash, R. Krishnamurti, G. A. Olah, . 1989, , 393. 2) M. Oishi, H. Kondo, H. Amii, . 2009, 1909. 3) S. Noritake, N. Shibata, S. Nakamura, T. Toru, M. Shiro, . 2008, 3465. 4) a) P. Eisenberger, S. Gischig, A. Togni, . 2006, , 2579. b) I. Kieltsch, P. Eisenberger, A. Togni, . 2007, , 754. c) P. Eisenberger, I. Kieltsch, N. Armanino, A. Togni, . 2008, 1575. d) K. Stanek, R. Koller, A. Togni, . 2008, , 7678. e) P. Eisenberger, I. Kiltsch, R. Koller, K. Stanek, A. Togni, . 2011, , 168. 5) a) B. R. Langlois, E. Laurent, N. Roidot, . 1991, , 7525. b) Y. Ji, T. Bruecki, R. D. Baxter, Y. Fujiwara, I. B. Seiple, S. Su, D. G. Blackmond, P. S. Baran, 2011, , 14411. c) Y. Fujiwara, J. A. Dixon, R. A. Rodriguez, R. D. Baxter, D. D. Dixon, M. R. Collins, D. G. Blackmond, P. S. Baran, . 2012, , 1494. d) Y. Fujiwara, J. A. Dixon, F. O'Hara, E. Daa Funder, D. D. Dixon, R. A. Rodriguez, R. D. Baxter, B. Herlé, N. Sach, M. R. 2012, Collins, Y. Ishihara, P. S. Baran, , 95.

24

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

Trifluoromethylthiolation

Synthetic Organic Chemistry

Trifluoromethylthiolation

Materials Chemistry

The trifluoromethylthio group (CF3S) has attracted attention as a potentially-significant functional group in the pharmaceutical and agrochemical fields because of its strong electron-withdrawing effect and high lipophilicity. Some methods for direct trifluoromethylthiolation have been developed1-4) and one of them, copper(I) trifluoromethanethiolate (CuSCF3) is an effective nucleophilic trifluoromethylthiolating reagent. On the other hand, a simple electrophilic reagent, trifluoromethylsulphenyl chloride (CF3SCl) is gaseous and highly toxic, so it is hardly used now. Recently, some electrophilic trifluoromethylthiolating reagents which are safer to use and easier to handle, have been reported. Both -methyl- -(trifluoromethylthio)aniline1) developed by Billard . and -(trifluoromethylthio)phthalimide4) developed by Rueping are useful electrophilic trifluoromethylthiolating reagents because their states are liquid and solid respectively. In addition, Shibata . have developed a hypervalent iodonium ylide having a trifluoromethanesulfonyl group 3, and used it for the electrophilic trifluoromethylthiolation. In this reaction, it seems that the trifluoromethylthiocation species generated by the reduction of 3 acts as an electrophilic trifluoromethylthiolating reagent for enamines, indoles and β-ketoesters.3) O O

CH3 Ph

N

N SCF3

SCF3

P2143 CF3

M2595 CH3

I

Nu

SCF3

CuCl, base dioxane, r.t.

T3143

O

S C C O

IPh 3 [P2143]

2 [T3143]

C1159 O

NuH

O

1 [M2595]

SO2CF3

Ph

N

SCF3

CF3SCu

O N SCF3 O

Product No.

Product Name

P2143 C1159 M2595 T3143

Benzoyl(phenyliodonio)(trifluoromethanesulfonyl)methanide Copper(I) Trifluoromethanethiolate N-Methyl-N-(trifluoromethylthio)aniline N-(Trifluoromethylthio)phthalimide

Unit Size 1g 1g 200mg 1g

5g 5g 1g 5g

References 1) a) F. Baert, J. Colomb, T. Billard, . 2012, , 10382. b) A. Ferry, T. Billard, E. Bacqué, B. R. Langlois, . 2012, , 160. c) Y. Yang, X. Jiang, F.-L. Qing, . 2012, , 7538. d) A. Ferry, T. Billard, B. R. Langlois, E. Bacqué, . 2009, , 8551. 2) X. Shao, X. Wang, T. Yang, L. Lu, Q. Shen, . 2013, , 3457. 3) Y.-D. Yang, A. Azuma, E. Tokunaga, M. Yamasaki, M. Shiro, N. Shibata, 4) R. Pluta, P. Nikolaienko, M. Rueping, . 2014, , 1650.

. 2013,

, 8782.

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

25

Formylation

Synthetic Organic Chemistry

Formylation

Materials Chemistry

Formyl group-containing compounds are important building blocks in organic synthesis since the formyl group can be transformed to other various functional groups. Aldehydes are the most typical formyl groupcontaining compound and are widely used as a substrate for carbon-carbon bond forming reactions such as the aldol reaction and the Wittig reaction.1-2) Also, their oxidation/reduction converts them to the related alcohols and carboxylic acids respectively, while the reductive amination is an efficient functional transformation of the formyl group into amines.3-5) As above reactions,the formyl group is a versatile precursor of organosynthetic reactions and a number of various formyl group introducing reagents have been developed. Reagents for the formylation are classified into three types according to their reactivity and substrates: (1) electrophilic aromatic substitution, (2) reaction with carbon nucleophiles, and (3) direct formylation at oxygen or nitrogen atoms. (1) Electrophilic aromatic substitution Vilsmeier-Haack Reaction Formylating Reagent

R

CHO

H

Duff Reaction

N

R Cl

Rieche Reaction

N

CH3 Cl

N

CH3 [C1545]

(also applicable to some electron-rich alkenes)

N

Cl N

Cl

OMe

[H0093]

[D1645]

(under acidic condition)

(with Lewis acid)

Formylating Reagents

Vilsmeier reagent is a strong electrophile and formylates electron-rich alkenes and aromatic rings by electrophilic aromatic substitution.6) This reagent is widely used and can be prepared by the reaction of DMF or -methylformanilide with phosphoryl chloride.7) The Duff reaction using hexamethylenetetramine is effective to formylate electron-rich aromatic compounds such as phenols and indoles.8) Furthermore, the Riecke reaction using dichloromethyl methyl ether is suitable for formylation at the sterically hindered site of substances.9) (2) Formylation by the reaction with carbon nucleophiles H

(1) formylating reagent

R M

R CHO

N

H3C N CHO

(2) H2O

EtO

OHC

H3C

M = Li, Mg etc.

O

CF3

TFEF

[D0722]

[T2586]

[E0495] formylating reagents

Formyl group-containing compounds can be also synthesized by the reaction of Grignard reagents or organolithium compounds with , -disubstituted formamides, orthoformates, -methoxymethyleneaniline and so on (Bouveault/ Bodroux-Chichibabin aldehyde synthesis).10,11) In addition, it is known that the direct -formylation of ketones can be performed by the reaction of related ketone enolates with TFEF.12) (3)

/ -Formylation R OH R1 NH R2

formylating reagent (base)

R OCHO

O

R1 NCHO R2

S

O N CHO

O

[F0854]

N NC

O

CHO

N N CHO

[F0356]

[B3920]

formylating reagents

-Formylsaccharin, cyanomethyl formate,13-15) and 1-formyl-1 -benzotriazole work as / -formylating reagents, and successfully react with alcohols and amines under mild conditions to afford the desired / -formylated compounds. Especially, -formylsaccharin can be used not only as a formylating reagent but also as a carbon monoxide introducing reagent (for more details, see the page 2.). 26

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

Formylation

B3920

C1545

F0356

D1645

D2344

N

N

H

C H

CH3

C N

Cl

CH3

Cl

O Cl

O

H

CN

Cl

CH3CH2 OCH3

CH3CH2

O

Synthetic Organic Chemistry

N

O

N C N CH OCH3

O

O0187

D0722

F0053

O

OCH2CH3

CH3

H C OPh OCH2CH3

N

O2N H

N

CH3

F0157

Cl

E0495

O NO2

F0234

O

H

F0854

G0393

O

O

C H

O

N

N H

OH

S

C H

O

O

O

H0093

M0552

N CH OCH2CH3

CH3

M1187

N O

P0018

CH3

O C H

CH3

N

CH3 N

N

Materials Chemistry

F0513

D4143

Cl

CH3

O0066

O N N

N

O

CH3 N C H N

N

N

C H

CH3

T2586

O0068

OCH2CH3 (CH2O)n

H C OCH2CH3 OCH2CH3

T3141 N

OCH3

O H

O

CF3

H C OCH3

N N

N

OCH3

Product No.

Product Name

B3920 C1545 F0356 D1645 D2344 O0187 D0722 D4143 F0053 E0495 F0513 F0157 F0234 F0854 G0393 H0093 M0552 M1187 P0018 O0066 T2586 O0068 T3141

1H-Benzotriazole-1-carboxaldehyde (Chloromethylene)dimethyliminium Chloride Cyanomethyl Formate Dichloromethyl Methyl Ether N-(Diethylcarbamoyl)-N-methoxyformamide Diethyl Phenyl Orthoformate N,N-Dimethylformamide 1-(2,4-Dinitrophenyl)pyridinium Chloride Ethyl Formate Ethyl N-Phenylformimidate Formic Acid 4-Formylmorpholine 1-Formylpiperidine N-Formylsaccharin Gold's Reagent Hexamethylenetetramine N-Methylformanilide N-Methyl-N-(2-pyridyl)formamide Paraformaldehyde Triethyl Orthoformate 2,2,2-Trifluoroethyl Formate Trimethyl Orthoformate Tris(1H-benzotriazol-1-yl)methane

N

N N N

N

Unit Size 1g 25g 5g 25g 5g 25mL 100mL 25mL 5g 25g 25mL 100mL 5g 5g 25g 25g 1g 25g 25mL 25mL 200mg

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

5g 250g 25g 250g 1g 25g 500mL 1g 500mL 25g 300mL 500g 500mL 25g 25g 500g 500g 5g 500g 500mL 5g 500mL 1g

27

Formylation

Synthetic Organic Chemistry

References 1) 2) 3) 4) 5) 6) 7) 8)

Materials Chemistry

9) 10) 11) 12) 13) 14) 15) 16) 17) 18) 19)

T. Mukaiyama, K. Narasaka, K. Banno, . 1973, 1011. S. G. Levine, . 1958, , 6150. Seyden-Penne,“Reductions by Alumino- and Borohydrides in Organic Synthesis”, 2nd ed., Wiley-VCH, New York, 1997. 1981, B. S. Bal, W. E. Childers Jr, H. W. Pinnick, , 2091. A. F. Abdel-Magid, K. G. Carson, B. D. Harris, C. A. Maryanoff, R. D. Shah, . 1996, , 3849. 2003, 138. a) Tasneem, b) R. A. Aungst Jr, C. Chan, R. L. Funk, . 2001, , 2611. A. Miyawaki, D. Kikuchi, M. Niki, Y. Manabe, M. Kanematsu, H. Yokoe, M. Yoshida, K. Shishido, . 2012, , 8231. a) J. C. Duff, E. J. Bills, . 1932, 1987. b) J. C. Duff, E. J. Bills, . 1934, 1305. c) J. C. Duff, E. J. Bills, . 1941, 547. d) J. C. Duff, E. J. Bills, . 1945, 276. 1960, A. Rieche, H. Gross, E. Höft, , 88. L. I. Smith, M. Bayliss, . 1941, , 437. L. I. Smith, J. Nichols, . 1941, , 489. G. H. Zayia, . 1999, , 989. 2011, 1920. T. Cochet, V. Bellosta, A. Greiner, D. Roche, J. Cossy, J. Deutsch, H.-J. Niclas, . 1993, , 1561. G. Bélanger, J. Boudreault, F. Lévesque, . 2011, , 6204. N. U. Hofsløkken, L. Skattebøl, . 1999, , 258. V. V. Mezheritskii, M. S. Korobov, O. M. Golyanskaya, N. I. Omelichkin, L. G. Minyaeva, G. S. Borodkin, A. A. Milov, A. V. Tsukanov, A. D. Dubonosov, . 2012, , 241. 1992, 1058. N. Akikusa, K. Mitsui, T. Sakamoto, Y. Kikugawa, 1978, 403. D. Comins, A. I. Meyers,

Zincke Aldehyde Synthesis (introduction of 4-formyl-1,3-butadienyl group) O2N

N H

SiMe3

Cl NO2

N

Zincke's salt (1) [D4143]

N SiMe3 1M NaOH aq.

N H

N H

CHO Y. 67%

N SiMe3

H

N H

KOt-Bu THF, 80 °C

N H H

NH

CHO

Y. 84%

CHO

Norfluorocurarine

1-(2,4-Dinitrophenyl)pyridinium chloride (Zincke salt, 1) reacts with secondary amines to afford the corresponding 5-amino-2,4-pentadienals (Zinke aldehydes).1) This type of reaction has been applied to the synthesis of various indole alkaloids.2) For example, Vanderwal . have reported the total synthesis of norfluorocurarine, a Strychnos alkaloid.3) 1) T. Zincke, W. Wurker, . 1905, 2) D. B. C. Martin, L. Q. Nguyen, C. D. Vanderwal, 3) D. B. C. Martin, C. D. Vanderwal,

28

, 107. . 2009,

. 2012, , 17. , 3472.

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

Cyanation

Synthetic Organic Chemistry

Cyanation

Materials Chemistry

A cyano group is a strong electron withdrawing group and a number of cyanating reagents are widely used in organic synthesis. The cyano group is converted to other functional groups such as carboxylic acids or amides by hydrolysis, and is also converted to amines or aldehydes by reduction with some reducing reagents. Furthermore, alkyl nitriles which are typical cyano group containing compounds are transformed into related ketones by reaction with carbon nucleophilic agents such as Grignard reagents or organolithium reagents. This synthetic method is efficient to synthesize the asymmetric ketones. On the other hand, the cyano group can be used for cycloaddition reactions with other multiple bonds. For instance, alkyl nitriles are additionally cyclized with azides to give the tetrazoles. As introducing methods for the cyano group, the reaction of potassium cyanide with alkyl halides is a typical synthetic method and the copper cyanide-mediated Sandmeyer reaction and the Rosenmundvon Braun reaction have been known for a long time. Recently, cyanation reactions using palladium catalysts with some cyanating reagents have been developed. In addition, benzyl thiocyanate1), ethyl cyanoacetate2), -butyl isocyanide3) and acetone cyanohydrin4) play as cyanide ion sources and can be used for the direct cyanation of various substances. Pd-catalyzed Cross-coupling Cyanation Using Boronic Acids

CH2SCN R B(OH)2

+

1)

Pd(PPh3)4 (cat.) CuTC

R CN

Dioxane [T0198]

CuTC =

CO2Cu

S

Pd-catalyzed Cyanation of Aryl Halides

X R

2)

O +

H3C

Pd(OAc)2 (cat.)

CN

O

CN

DPPE, TMEDA, DMF

R

[C0441]

X = Cl, Br, I

Pd-catalyzed C-H Cyanation

CH3 Ar

H

+

H3C

NC

3)

Pd(OAc)2 (cat.) Cu(TFA)2

Ar

CN

CH3 [B1274]

H Ar

H : R1

R3

N

R

N R2

H

Pd-catalyzed Cyanation of Alkenyl Halides 4)

R2 X

R1 R3

X = Cl, Br, I

CH3 +

HO

CN CH3 [M0361]

Pd2(dba)3 (cat.) DPPP, Na2CO3 Et2O/DMA

R2 CN

R1 R3

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

29

Cyanation

Synthetic Organic Chemistry

M0361

T0198

B1274 CH2SCN

CH3

Cl

CH3 C NC

CH3

C1952 CH2SCN

CH3

HO C CN

CuCN

CH3

C1242

C0441 O

P1613

T1046

NC

OCH2CH3

T0990 CH3

O

O

NC P OCH2CH3

Materials Chemistry

C3003

O

CH3

Product No.

Product Name

M0361 T0198 B1274 C3003 C1952 C1242 C0441 P1613 T1046 T0990

Acetone Cyanohydrin Benzyl Thiocyanate tert-Butyl Isocyanide 2-Chlorobenzyl Thiocyanate Copper(I) Cyanide Diethyl Cyanophosphonate Ethyl Cyanoacetate Potassium Cyanide p-Toluenesulfonylmethyl Isocyanide Trimethylsilyl Cyanide

KCN

CH3

S CH2NC O

CH3

Si CN CH3

Unit Size 25mL 500mL 25g 500g 5mL 25mL 1g 5g 25g 300g 5g 25g 25g 500g 25g 5g 25g 25mL 100mL 500mL

References 1) 2) 3) 4)

30

Z. Zhang, L. S. Liebeskind, . 2006, , 4331. S. Zheng, C. Yu, Z. Shen, . 2012, , 3644. J. Peng, J. Zhao, Z. Hu, D. Liang, J. Huang, Q. Zhu, K. J. Powell, L.-C. Han, P. Sharma, J. E. Moses,

. 2012, , 4966. . 2014, , 2158.

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

Amination

Synthetic Organic Chemistry

Amination The Gabriel reagent is widely used as a nucleophilic aminating agent since its reactivity is reliable and its handling is easy.1) A variety of aminating agents analogous to the Gabriel reagent have been reported. The potassium salt of imide 1 reacts with alkyl halide to give imide 2. 2 is treated with base or acid to give either -Boc-amine 3 or -methoxycarbonylamine 4, respectively. Moreover, 1 also serves as an acid nucleophile in the Mitsunobu reaction to allow for the conversion of hydroxy groups to amino groups. Therefore, 1 is a useful reagent to give monoprotected amines.2) O

O t-BuO C

NaOH aq. / MeOH

NH , KOH

MeO C O

R CH2N

C Ot-Bu H

C Ot-Bu

3

Materials Chemistry

1 [I0510]

R CH2Br

R CH2N

O C OMe O

CF3CO2H

2

R CH2N

H C OMe O

4

Fukuyama and co-workers have demonstrated various reactions using the -substituted sulfonamide 5.3) Smooth reactions of 5 occur with alkyl halides under basic conditions and alcohols under Mitsunobu conditions to provide -nitrobenzenesulfonyl ( -Ns) amines 6. The various -Ns amines (Alloc, Boc, Cbz) 6 obtained from these reactions can be selectively deprotected, under the appropriate conditions, to afford the monoprotected amines 7 and 8. Furthermore, 7 can be converted to the primary amine in high yields via a second deprotection. 8 can be converted to the secondary amine in high yields by repeating the alkylation and deprotection process.4) RS -

R1 SO2NHY

a)

NO2

R1NH2

7

N Y

O2S

b)

R1NHY SO2NHR1

NO2

NO2

b)

i) c) ii) RS -

5

6

R1NHR2

8

Y = Alloc 5a [A1632] a) R1X, K CO , DMF 2 3 Boc 5b [B2303] or Cbz 5c [C1757] 1 R OH, DEAD, PPh3

c) R2X, K2CO3, DMF or R2OH, DEAD, PPh3

b) When 5a Pd(PPh3)4, pyrrolidine 5b TFA 5c BCl3

On the other hand, acetoxime -(2,4,6-trimethylphenyl)sulfonate 9 has been reported as a useful electrophilic aminating agent. 9 reacts with Grignard reagents in the presence of a catalytic amount of magnesium chloride to afford primary amines in good yields.5)

Me

R MgBr

A1441

A1632 CH3 O

CH3

Me O Me S O N C Me O Me 9 [A1441] , MgCl2 (cat.)

S O N C O CH3

A1137 O

CH3 CH3

R N C

SO2NH C OCH2CH NO2

CH2

Hydrolysis

Me Me

A2457 N

R NH2

A1341

N

N

N

N

NH2

CH3

CH3 N3

S CH2N3 PF6

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

31

Amination

Synthetic Organic Chemistry

B3380

B2303

B1648 O

Br O

SO2NH

CH3 C C NH2

B2857

I0510

O SO2NH C OtBu

C OtBu

O CH3 H P O N C O C CH3

O

O

NO2

CH3O 2

CH3

CH3

O

CH3O C NH C OtBu

CH3

C1757

I0497

B1734

D2361

D1899

O SO2NH

C OCH2

NO2

tBuO

Materials Chemistry

D1672

O

O

O

C NH

C OtBu

M1182

P O

O

H0258

OCH2CH3

N

CH3

N

H2N OH

N

P1235

M0886 M0343

CH3ONH2

O

N H

OCH3

. HCl

. HCl

H2N OH

O

. H2SO4

O

O

N H

2

D2479

H C

N N

. HCl

H0196

P0403 O

O H2N O S OH

CH3

OCH2CH3

OCH2CH3

CH3

H0530

H2N P OCH2CH3

N

O S O N C

CH3

N3

BuO C NH P OCH2CH3

H0093 CH3

O O

O

O

t

NK

NNa H C

O

O

T1184 CH3 CH3

Si

CH2N3

CH3

32

Product No.

Product Name

A1441 A1632 A1137 A2457 A1341 B3380 B2303 B1648 B2857 I0510 C1757 I0497 B1734 D2361 D1899 D1672 M1182 H0093 H0258 H0196 H0530 M0886 M0343 P1235

Acetoxime O-(2,4,6-Trimethylphenylsulfonate) N-Allyloxycarbonyl-2-nitrobenzenesulfonamide 4-Amino-1,2,4-triazole 2-Azido-1,3-dimethylimidazolinium Hexafluorophosphate Azidomethyl Phenyl Sulfide 2-Bromoisobutyramide N-(tert-Butoxycarbonyl)-2-nitrobenzenesulfonamide N-(tert-Butoxycarbonyl)-p-toluenesulfonamide tert-Butyl [Bis(4-methoxyphenyl)phosphinyloxy]carbamate tert-Butyl Methyl Iminodicarboxylate N-Carbobenzoxy-2-nitrobenzenesulfonamide Di-tert-butyl Iminodicarboxylate Diethyl N-(tert-Butoxycarbonyl)phosphoramidate Diethyl Phosphoramidate N,O-Dimethylhydroxylamine Hydrochloride Diphenylphosphoryl Azide Ethyl O-Mesitylsulfonylacetohydroxamate Hexamethylenetetramine Hydroxylamine Hydrochloride Hydroxylamine Sulfate Hydroxylamine-O-sulfonic Acid O-Methylhydroxylamine Hydrochloride (ca. 40% in Water, ca. 5.4mol/L) O-Methylhydroxylamine Hydrochloride Phthalimide DBU Salt

Unit Size 5g 25g

1g

5g 5g 10g 1g 5g 5g

25g 5g 1g

25g 25g

100g 25g 5g 25g 25g 25g 100g 25mL 100g

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

25g 5g 250g 5g 5g 25g 25g 25g 5g 5g 25g 25g 5g 25g 500g 250g 25g 500g 500g 500g 500g 500mL 500g 25g

Amination

Product Name

P0403 D2479 T1184

Phthalimide Potassium Salt Sodium Diformylamide Trimethylsilylmethyl Azide

Unit Size 25g 1g

Synthetic Organic Chemistry

Product No.

500g 25g 5g

References

1968, , 919; U. Ragnarsson, 1) S. Gabriel, . 1887, , 2224; M. S. Gibson, R. W. Bradshaw, L. Grehn, . 1991, , 285. 2) J. D. Elliott, J. H. Jones, . 1977, 758; C. T. Clarke, J. D. Elliott, J. H. Jones, 1978, 1088; J. M. Chong, S. B. Park, . 1993, , 7300. 1999, 1301. 3) T. Fukuyama, M. Cheung, T. Kan, 2002, 4) T. Kan, A. Fujiwara, H. Kobayashi, T. Fukuyama, , 6267. 5) E. Erdik, M. Ay, . 1989, , 663.

Materials Chemistry

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

33

Mitsunobu Reaction

Synthetic Organic Chemistry

Mitsunobu Reaction O

O H EtO C N

O

EtO C N N C OEt OH

R1

R3

HO

+

O H N C OEt

R2

R3

O

R1 R2

O

O

O PPh3

PPh3

Materials Chemistry

The Mitsunobu reaction is a unique dehydration-condensation reaction of alcohols with various organic acids, which together with azodicarboxylate esters and triphenylphosphine are generally used as dehydration-condensation reagents.1) The Mitsunobu reaction is carried out under mild conditions and alcohols with a chiral center are inverted with the Walden-inversion. Acid components such as carboxylic acids, phenols, active methylene compounds and imides are applicable for this transformation. Therefore, the Mitsunobu reaction is one of the most useful synthetic methods in organic synthesis. O R R

R

O

O

N H

O

O

R1

R2

EWG

R1

R2

OH

O

EWG

O R1

R

EWG

EWG

OH R1

R2 HO CN R1

CN

OH

R1

R1 R

O R

R

R2

R

Ns N

R1

X

S R1

R2

Ns

SH O

R2

N H

O

N3

DPPA R2

N

R2

R1

R2

R2

Also, synthetic applications of the Mitsunobu reaction have been widely studied due to its excellent chemical reactivity and various improved synthetic methods have been reported as follows.2) 1) The basicity of the azodicarboxyamide derivatives is higher compared to that of azodicarboxylate esters, and its chemical property expands the availability of the acids into weaker acids with high p a value. In addition, after the reactions, these reagents can be easily removed by column chromatography or extraction because they are high-polarity molecules.3) O

O

N C N N C N O

O

ADDP [A1051]

EtO C N N C OEt DEAD [A0705]

O

Easy to remove because of high-polarity molecule O

N C N N C N TMAD [A1458]

34

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Mitsunobu Reaction

Synthetic Organic Chemistry

2) By using phosphines with a base moiety4) or diphenylphosphinopolystyrene resins5) instead of triphenylphosphine, the generated phosphine oxides can be easily removed. In addition, phenoxydiphenylphosphine is an effective agent when sterically hindered tertiary alcohols are employed.6) Ph P Ph triphenylphosphine [T0519]

Ph

Ph

P

N

Ph

P Ph

O P

Ph [D2766]

[D2478]

Separable by extraction

Ph [P1843]

Separable by filtration

Materials Chemistry

N Ph [D2471]

Ph

P

Applicable to tertiary alcohols

3) Tsunoda . have reported that cyanomethylene tributyl phosphorane is an effective agent for improving the Mitsunobu reaction.7) It plays roles of both azodicarboxylate esters and tributylphosphine independently, and enables the Mitsunobu reaction to proceed even when using nucleophiles such as active methylene compounds with high p a values as well as typical organic acids. However, it is necessary to pay attention when this reagent is used with ketones or aldehydes because it behaves like a Wittig reagent.8)

Bu3P

O CN

O

EtO

[C1500]

OEt

NC

SO2Ph

pKa = 12.0

pKa = 13.3

MeS

SO2Tol

pKa = 23.4

4) It has been reported that the stoichiometry used for the amounts of azodicarboxylate esters can be reduced to catalytic amounts of one by using iodobenzene diacetate or iron phthalocyanine as a reoxidant.9) This method can reduce the hydrazide by-product to a minimum.

A1458

Azodicarboxylates & Amides

A1332

A0776

O

O

Cl3CH2CO C N N C OCH2CCl3

A1051

O Me2N

O

O

C N N C

NMe2

D3544

O

O

BnO C N N C OBn

O

N C N N C N

A0705

O t

B3364

O

BuO C N N C OtBu

O O CH3OCH2CH2O C N N C OCH2CH2OCH3

A1246

O

O

EtO C N N C OEt

O iPrO

O

C N N C OiPr

A0882

O

O

MeO C N N C OMe

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

35

Synthetic Organic Chemistry

Mitsunobu Reaction

Product No.

Product Name

A1458 A1051 B3364 A1332 A0776 D3544 A0705 A1246 A0882

1,1'-Azobis(N,N-dimethylformamide) 1,1'-(Azodicarbonyl)dipiperidine Bis(2-methoxyethyl) Azodicarboxylate Bis(2,2,2-trichloroethyl) Azodicarboxylate Dibenzyl Azodicarboxylate (40% in Dichloromethane, ca. 1.7mol/L) Di-tert-butyl Azodicarboxylate (20% in Toluene) Diethyl Azodicarboxylate (40% in Toluene, ca. 2.2mol/L) Diisopropyl Azodicarboxylate (40% in Toluene, ca. 1.9mol/L) Dimethyl Azodicarboxylate (40% in Toluene, ca. 2.7mol/L)

Unit Size

Materials Chemistry

D2411

1g 5g

25g 25g

D1019

5g 25g 5g 5g 25g 25g 250g 250g 25g

100g 100g

D2478

Et

Phosphines (Mitsunobu Reaction)

D2766

D2471

CH2

P

P

T0361

P1843

CH3

T1165

Bu

P

T1005

T0503 (CH2)5CH3

P

P

O P

t

Bu

P tBu

Bu Bu

T1912

t

CH

CH3

N

P

Et

I0583

P

(CH3)2N

P

P

CH3(CH2)5 P

Bu

(CH2)5CH3

T0519 (CH2)7CH3

CH3(CH2)7 P

P

(CH2)7CH3

Product No.

Product Name

D2411 D1019 D2478 D2766 D2471 I0583 P1843 T1912 T0361 T1165 T1005 T0503 T0519

Dicyclohexylphenylphosphine 1g 5g Diethylphenylphosphine 1mL 5mL 4-(Dimethylamino)phenyldiphenylphosphine 1g 5g 4-Diphenylphosphinomethyl Polystyrene Resin cross-linked with 2% DVB (200-400mesh) (0.5-1.0mmol/g) 5g Diphenyl-2-pyridylphosphine 1g 5g Isopropyldiphenylphosphine 1g 5g Phenoxydiphenylphosphine 5g 25g 5g Tri-tert-butylphosphine Tributylphosphine 25mL 100mL 500mL 25mL Tricyclohexylphosphine (contains Tricyclohexylphosphine Oxide) (ca. 18% in Toluene, ca. 0.60mol/L) Trihexylphosphine 25mL Tri-n-octylphosphine 25mL 100mL 500mL Triphenylphosphine 25g 500g

Unit Size

C1500

Modified New Mitsunobu Reaction (Tsunoda Reagent)

36

Bu Bu

P CH CN Bu

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Mitsunobu Reaction

Product Name

C1500

Cyanomethylenetributylphosphorane

Unit Size 1g

5g

Synthetic Organic Chemistry

Product No.

25g

References

. 1995,

, 2531.

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

Materials Chemistry

1981, 1. 1) O. Mitsunobu, 1999, number 2) T. Onozawa, , 10. 3) a) T. Tsunoda, Y. Yamamiya, S. Ito, . 1993, , 1639. b) T. Tsunoda, J. Otsuka, Y. Yamamiya, S. Ito, . 1994, 539. c) S. Ito, T. Tsunoda, . 1994, , 2071. d) T. Tsunoda, Y. Yamamiya, Y. Kawamura, S. Ito, . 1995, , 2529. 4) a) L. D. Arnold, H. I. Assil, J. C. Vederas, . 1989, , 3973. b) A. R. Tunoori, D. Dutta, G. I. Georg, . 1998, , 8751. 5) R. A. Amos, R. W. Emblidge, N. Havens, . 1983, , 3598. 2010, 6) Review: T. Mukaiyama, K. Kuroda, Y. Maruyama, , 63. 7) T. Tsunoda, M. Nagaku, C. Nagino, Y. Kawamura, F. Ozaki, H. Hioki, S. Ito, 8) T. Tsunoda, H. Takagi, D. Takaba, H. Kaku, S. Ito, . 2000, , 235. 9) a) T. Y. S. But, P. H. Toy, . 2006, , 9636. b) D. Hirose, T. Taniguchi, H. Ishibashi. . 2013, , 4613.

37

Condensation & Active Esterification

Synthetic Organic Chemistry

Condensation & Active Esterification

Materials Chemistry

The synthesis of carboxylic esters is one of the most fundamental and important processes for producing useful compounds in organic chemistry. The classical esterification reaction is condensation of a carboxylic acid and an alcohol under acidic conditions. This is an equilibrium reaction, and in order to effectively generate the ester, the equilibrium need to be shift toward the ester. To achieve this equilibrium shift requires adding one of the substrates in large excess and the removal of the generated water by distillation. However, when both carboxylic acid and alcohol are expensive and not easily available, it is not economical to use one of the substrates in large excess. Thus the classical esterification method is not the best method to use in such a case. Furthermore, when the substrate is unstable to heat, the classical method does not always yield the desired results. Since esterification is a basic reaction that is applied to many different types of substrates, there is a need for alternative methods which proceed under mild conditions without the need for using large excess of one of the substrates. Over the years, there has been much research done by many chemists, and many useful methods have been reported. NO2 O

O

NO2

O Me Me

O R1

OH

+

(1.0 eq.)

NO2 O

O

1 [M1439] (1.1 eq.)

R2OH

R1

Et3N (1.1 eq.), DMAP (0.1 eq.), rt

OR2

+

OR2

Me

(1.1 eq.)

Ester A R1COOH

Ester B

R2OH PhCH2 THPO(CH2)5 CH2=CHCH2 C9H19C(CH3)2

Ph(CH2)2 Ph(CH2)2 Ph(CH2)2 Ph(CH2)2

Y. %

Ester A / Ester B

95 98 92 94

>200 >200 >200 >200

Shiina and co-workers have reported a method using 2-methyl-6-nitrobenzoic anhydride (1). This esterification procedure is quite simple. Triethylamine, a catalytic amount of 4-dimethylaminopyridine, and 1 were dissolved in a solvent. The carboxylic acid was added and stirred, and finally a nearly equimolar amount of alcohol was added and the reaction stirred under room temperature. Through this reaction process, the desired ester (ester A) is obtained in high yields. The nitro group on the condensation reagent 1 promotes and facilitates the esterification under room temperature. The introduction of substituents at the two ortho positions of benzene ring controls the generation of byproduct (ester B). These two effects synergistically act to produce the desired ester in excellent yield and high purity. This reaction can also be applied to intramolecular esterification, and can afford lactones in high yields.

A1797

A1861

B3816

B1774 N

N

N

N

N

N

N

O C

N(CH3)2

PF6

N

O C

N(CH3)2

B1657

BF4

N

N

N

N

N(CH3)2

PF6

N

N

O C

N

O

N

N(CH3)2

B2771

N N(CH3)2

N

O C N

N(CH3)2

B1658

O C

38

N

N

B1651 N

PF6

PF6

N

N N

OP[N(CH3)2]3

B1213

N(CH3)2 N(CH3)2

BF4

CH3

O

O O

CH2 N C N CH2

O

CH3

O

B3604 F

N P N

CH3

O

PF6

N

O CH3

N

P N

Cl

O O

F

F

F

O F

O C O F

F

F F

F

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Condensation & Active Esterification

B3817

B3927

N

N C O N PF6

O

B0832

CH3

CH2O C O N

CH3 CH3

O

O

Cl

CH3

N

C1131 N

N

N

PF6

N(CH3)2

N

Cl

O

O

O

N(CH3)2

C0903

O

N

N

Cl N

Cl

N

CH3

O

C0906

N

N C N

O

CH3

N

CH2O C O N

BF4

O

CH3

C1651

O N(CH3)2

N N

C

C1639 C1408

Cl

O C

N(CH3)2

C0905

N

O

N

O C

O O

N

O

CH3

C1926

Cl

CH2O C O N

O C O C CH3

C0119

Materials Chemistry

C1988

CH3

O

CH3

Cl

N

C1362

Cl O

Br

PF6

N P Br

BF4

CH2CH3

C1124

CH3 C CH3 ClO4

N

O

C1574

N

N

O

N CH3 CH3

B2680

O

Br

B(OH)2 CH3 CH3

CH3 CH3

N

B1036

Synthetic Organic Chemistry

O

C1298

CH3 PF6

Cl

CH3

C1379

C1375

SO3 CH2CH3

N

BF4

O

Cl

Cl

N

I N

CH3

C1957

CH3

N

CH3

CH3

N

N

PF6

CH3CH2O C

N P Cl

NC

PF6

C N O C

D0436

O

O N

N

D1393

Bu

N

C1242

N C N

Bu

N(CH3)2

O P

Bu

D0254

N

CH3

OH

N

N

N

D3293

C N SO3

O

O

OCH2CH3

N

CH2CH2N

D3263

NC P OCH2CH3

OCH2CH3

N

O

D2039 O

OCH2CH3

CH3

P CH CN

PF6

D3262

BF4

C0793

O

N

Cl

N

Cl

C1500 O

CH3

C

CH3

C2733 N

N

PF6

Cl

CH3

C2551

N

C

Cl

N

D2919

O C

N

N(CH3)2 N(CH3)2

BF4

D4029 OCH3

CH3

N O

CH3

N

SO3

CH3

CH3 N C N

CH3

CH3

CH3

F NH2

F

F

F

2

N CH3O

N N

N

CH3

CH3CH2 N C N

(CH2)3N

Cl

F

CH3 CH3

O

D1601

CH3CH2 N C N

D1450

(CH2)3N

CH3

D2898 N

CH3

. HCl

D2899

SO3

CH3 CH3

N N

N

D1771

CH3

CH3 N C

N CH2OH

H CH2

N CH3

CH3 N C

CH2OH

H CH2

CH3

N H

CH3

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

CH3

39

Condensation & Active Esterification

Synthetic Organic Chemistry

D3683

D2038

D1720

D1672

D2201 O

O

O

NH2

. CF3SO3

N

C N

P O

O

2

O

O

O N3

S

S O

OCH3

C1407

D1114

O

P O

D2477

T1906

O

D1662 O

O O

O N

N

O C O

N

N

S

S

S

S

S

N

N

N O C O N

O C O

N

N O

Materials Chemistry

D2222

E0916

O2 N

NO2 N

S S

E0363

E0847

C N O C

N(CH3)2

N

N(CH3)2

NC

OCH2CH3

C OCH2CH3

BF4

F0726

N

CH3

F

H0468 CH3

CH3

N

N

CH3

PF6

O

O

OH

N

O

OH

M1439

NOH

N OH O

M0071

M0670 SO2Cl

CH3 CH3

SO2Cl CH3

N

CH3 O

CH3

N CH3

CH3

SO2Cl

M1116

O

O

M1186 SO3Na

N

. H2O

OH

H1304

O

H0395 O

N

N

CH2O C O N

CH3

O

N

CH3

B0249 H0623

O

H0528

F

CH3

O

NOH

O

SO3

O

O

NC

F0225

F0239

O CH3CH2O C

N

O

T0681

N0477

N0634

O NO2 O

O

NO2

O C CF3

CH3

O

N O

Me Me

N H

N

O

NO2

N N

O

CH3 N CH3

N

O C N CH3

BF4

CH3

NO2

O0200

O0390

T0648

P1626

P2231

O N

O O

BF4

N O

N C C N

N O C

O C CCl3 Cl

F

Cl

F

Cl

O CH3SO3

P

O

OSO2CH3

40

P1768

P1320 P1319

SO2CH3 n

O CH2CH2CH3 P O CH3CH2CH2 O P P O CH2CH2CH3 O

F

S O O

F

P0939 O

O

F

F

Q0016

N

C O C

O

F

O O2N

F

Cl

P1042

F

F CF3SO3

N(CH3)2 N(CH3)2

NH3

Cl

N N

N

SO2Cl N

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Condensation & Active Esterification

S0836

T1562

T2908

CH3

F

B(OH)2 CH3 CH3

CH3

N F

CH3

F

CH3

OH

T1017

T1985

O

O N O C

CH3 CH3

SO2Cl

T2224

N(CH3)2 N(CH3)2

PF6

N O C

T1413

N

N N H

N

N

SO2

N H

CH3

Cl

N

Cl

Cl Cl Cl

Cl

T0459 CH3 O

CF3

CH3

O

C O C

T1122 SO2Cl

CH

CH

CH3

SO3

CH3

CH3

Materials Chemistry

T1593

CF3

CH

CH3 CH3

CH3

N H

CH3

CH3

Product No.

Product Name

A1797 A1861 B3816 B1774 B1651 B1657 B1658 B2771 B1213 B3604 B3817 B3927

O-(7-Azabenzotriazol-1-yl)-N,N,N ',N '-tetramethyluronium Hexafluorophosphate O-(7-Azabenzotriazol-1-yl)-N,N,N ',N '-tetramethyluronium Tetrafluoroborate O-(Benzotriazol-1-yl)-N,N,N ',N '-bis(pentamethylene)uronium Hexafluorophosphate 1H-Benzotriazol-1-yloxytripyrrolidinophosphonium Hexafluorophosphate 1H-Benzotriazol-1-yloxytris(dimethylamino)-phosphonium Hexafluorophosphate 5g O-(Benzotriazol-1-yl)-N,N,N ',N '-tetramethyluronium Hexafluorophosphate 5g O-(Benzotriazol-1-yl)-N,N,N ',N '-tetramethyluronium Tetrafluoroborate 1,3-Bis(2,2-dimethyl-1,3-dioxolan-4-ylmethyl)carbodiimide (This product is only available in Japan.) Bis(2-oxo-3-oxazolidinyl)phosphinic Chloride Bis(pentafluorophenyl) Carbonate N,N,N ',N '-Bis(tetramethylene)-O-(N-succinimidyl)uronium Hexafluorophosphate 2,6-Bis[(2,2,6,6-tetramethyl-1-piperidinyl)methyl]phenylboronic Acid (contains varying amounts of

C1298 B1036 B2680 B0832 C1574 C1124 C1362 C0119 C1988 C1926 C1131 C1639 C1408 C1651 C0905 C0903 C0906 C1379 C1375 C1957 C2551 C2733

N-(2-Bromobenzyloxycarbonyloxy)succinimide 2-Bromo-1-ethylpyridinium Tetrafluoroborate Bromotripyrrolidinophosphonium Hexafluorophosphate N-tert-Butyl-5-methylisoxazolium Perchlorate tert-Butyl 2,4,5-Trichlorophenyl Carbonate N-Carbobenzoxyoxysuccinimide 2,2'-Carbonylbis(3,5-dioxo-4-methyl-1,2,4-oxadiazolidine) 1,1'-Carbonyldiimidazole O-(6-Chlorobenzotriazol-1-yl)-N,N,N ',N '-tetramethyluronium Hexafluorophosphate O-(6-Chlorobenzotriazol-1-yl)-N,N,N ',N '-tetramethyluronium Tetrafluoroborate N-(2-Chlorobenzyloxycarbonyloxy)succinimide 2-Chloro-1,3-dimethylimidazolinium Chloride (ca. 25% in Dichloromethane) 2-Chloro-1,3-dimethylimidazolinium Chloride 2-Chloro-1,3-dimethylimidazolinium Hexafluorophosphate 2-Chloro-3-ethylbenzoxazolium Tetrafluoroborate 2-Chloro-1-methylpyridinium Iodide 2-Chloro-1-methylpyridinium p-Toluenesulfonate 1-(Chloro-1-pyrrolidinylmethylene)pyrrolidinium Hexafluorophosphate 1-(Chloro-1-pyrrolidinylmethylene)pyrrolidinium Tetrafluoroborate Chloro-N,N,N ',N '-tetramethylformamidinium Hexafluorophosphate Chlorotripyrrolidinophosphonium Hexafluorophosphate (1-Cyano-2-ethoxy-2-oxoethylidenaminooxy)dimethylaminomorpholinocarbenium Hexafluorophosphate (This product is only available in Japan.) Cyanomethylenetributylphosphorane 1-Cyclohexyl-3-(2-morpholinoethyl)carbodiimide Metho-p-toluenesulfonate N,N '-Dicyclohexylcarbodiimide 3-(Diethoxyphosphoryloxy)-1,2,3-benzotriazin-4(3H)-one Diethyl Cyanophosphonate 3,4-Dihydro-3-hydroxy-4-oxo-1,2,3-benzotriazine

C1500 C0793 D0436 D3262 C1242 D2039

BF4

OH

C Cl

N

N(CH3)2

T0389 O

N

N(CH3)2

O

O

T0340

Synthetic Organic Chemistry

SO2Cl

SO3Na F

T2929

Unit Size

Anhydride)

5g 1g 1g 5g 25g 25g 5g 5g 1g 200mg 5g 5g 1g 25g 25g 1g 5g

5g 5g 5g

5g 1g 5g 1g

5g 5g 25g 5g 10g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

25g 5g 5g 25g 100g 100g 25g 1g 25g 5g 5g 1g 10g 25g 25g 5g 5g 250g 5g 250g 5g 25g 10g 25g 25g 25g 25g 25g 25g 25g 5g 5g 25g 5g 25g 25g 400g 5g 25g 25g

41

Synthetic Organic Chemistry

Condensation & Active Esterification

Product No.

Product Name

D3263

O-(3,4-Dihydro-4-oxo-1,2,3-benzotriazin-3-yl)-N,N,N ',N '-tetramethyluronium Tetrafluoroborate 5g 25g 5g 25g 3,4-Dihydro-2H-pyrido[1,2-a]pyrimidin-2-one N,N '-Diisopropylcarbodiimide 25g 250g Dimesitylammonium Pentafluorobenzenesulfonate 1g 5g 4-(4,6-Dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium Chloride 5g 25g 1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide 5g 25g 1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide Hydrochloride 5g 25g 250g 4-Dimethylaminopyridine 25g 100g 500g 100mg (4R,5R)-1,3-Dimethyl-4,5-diphenyl-2-[(S)-1-benzyl-2-hydroxyethylimino]imidazolidine (4S,5S)-1,3-Dimethyl-4,5-diphenyl-2-[(R)-1-benzyl-2-hydroxyethylimino]imidazolidine 100mg 2,6-Dimethylpyridinium p-Toluenesulfonate 25g Diphenylammonium Trifluoromethanesulfonate 1g 5g 25g Diphenyl (2,3-Dihydro-2-thioxo-3-benzoxazolyl)phosphonate 5g 25g N,N-Diphenyl-4-methoxybenzamide 5g Diphenylphosphoryl Azide 5g 25g 250g 4,6-Diphenylthieno[3,4-d]-1,3-dioxol-2-one 5,5-Dioxide 5g Di-2-pyridyl Carbonate 5g 2,2'-Dipyridyl Disulfide 5g 25g 250g 4,4'-Dipyridyl Disulfide 5g 25g O,O '-Di-2-pyridyl Thiocarbonate 1g Di(N-succinimidyl) Carbonate 5g 25g 2,2'-Dithiobis(5-nitropyridine) 5g O-[(Ethoxycarbonyl)cyanomethyleneamino]-N,N,N ',N '-tetramethyluronium Tetrafluoroborate 1g 5g 1-Ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline 25g Ethyl Cyano(hydroxyimino)acetate 25g N-[(9H-Fluoren-9-ylmethoxy)carbonyloxy]succinimide 5g 25g 2-Fluoro-1-methylpyridinium p-Toluenesulfonate 5g 25g Fluoro-N,N,N ',N '-tetramethylformamidinium Hexafluorophosphate 1g 5g 25g 200g 500g 1-Hydroxybenzotriazole Monohydrate N-Hydroxy-5-norbornene-2,3-dicarboximide 25g 250g N-Hydroxyphthalimide 25g 100g 500g N-Hydroxysuccinimide 25g N-Hydroxysuccinimide 25g 100g 500g N-Hydroxysulfosuccinimide Sodium Salt 200mg 1g 2,4-Mesitylenedisulfonyl Dichloride 5g 25g 2-Mesitylenesulfonyl Chloride 25g 500g 9-Methyl-3,4-dihydro-2H-pyrido[1,2-a]pyrimidin-2-one 25g 2-Methyl-6-nitrobenzoic Anhydride 1g 5g 25g 5g 6-Methyl-2H-pyrido[1,2-a]pyrimidin-2-one 4-Nitrophenyl Trifluoroacetate 5g 25g 3-Nitro-1,2,4-triazole 5g 2-(5-Norbornene-2,3-dicarboximido)-1,1,3,3-tetramethyluronium Tetrafluoroborate 5g 25g 1,1'-Oxalyldiimidazole 1g 5g O-[2-Oxo-1(2H)-pyridyl]-N,N,N ',N '-tetramethyluronium Tetrafluoroborate 1g 5g Pentachlorophenyl Trichloroacetate 25g Pentafluoroanilinium Trifluoromethanesulfonate 1g 5g 25g Pentafluorophenyl 4-Nitrobenzenesulfonate 1g 5g Phosphorus Pentoxide - Methanesulfonic Acid 25g 500g 25g Propylphosphonic Acid Anhydride (Cyclic Trimer) (48% in N,N-Dimethylformamide, ca. 1.6mol/L) Propylphosphonic Acid Anhydride (Cyclic Trimer) (50% in Ethyl Acetate, ca. 1.7mol/L) 25g 100g 3-Pyridinecarboxylic Anhydride 1g 5g 4-Pyrrolidinopyridine 5g 25g Quinoline-8-sulfonyl Chloride 5g 25g Sodium 2,3,5,6-Tetrafluoro-4-hydroxybenzenesulfonate 1g 5g 2,4,5,6-Tetramethylbenzenedisulfonyl Dichloride 5g 1g 2-[(2,2,6,6-Tetramethyl-1-piperidyl)methyl]phenylboronic Acid (contains varying amounts of Anhydride) N,N,N ',N '-Tetramethyl-O-(N-succinimidyl)uronium Hexafluorophosphate 5g 25g N,N,N ',N '-Tetramethyl-O-(N-succinimidyl)uronium Tetrafluoroborate 1g 5g 1H-Tetrazole 5g 25g 1-(p-Toluenesulfonyl)imidazole 5g 25g 1,2,4-Triazole 25g 100g 500g 2,4,6-Trichlorobenzoyl Chloride 5g 25g 2,4,5-Trichlorophenol 25g 500g 4-Trifluoromethylbenzoic Anhydride 10g 2,4,6-Triisopropylbenzenesulfonyl Chloride 25g 500g 25g 2,4,6-Trimethylpyridinium p-Toluenesulfonate

Materials Chemistry

D1393 D0254 D3293 D2919 D4029 D1601 D1450 D2898 D2899 D1771 D3683 D2038 D1720 D1672 D2201 C1407 D1114 D2477 T1906 D1662 D2222 E0916 E0363 E0847 F0239 F0225 F0726 H0468 H0528 H0395 B0249 H0623 H1304 M1186 M0071 M0670 M1439 M1116 T0681 N0477 N0634 O0200 O0390 T0648 P1626 P2231 P1042 P1320 P1319 P1768 P0939 Q0016 S0836 T1562 T2908 T2929 T2224 T1017 T1985 T0340 T1413 T0389 T1593 T0459 T1122

42

Unit Size

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Condensation & Active Esterification

References Synthetic Organic Chemistry

1) 2) 3) 4) 5) 6) 7)

I. Shiina, R. Ibuka, M. Kubota, . 2002, 286. I. Shiina, M. Kubota, R. Ibuka, . 2002, , 7535. J. Tian, N. Yamagiwa, S. Matsunaga, M. Shibasaki, . 2003, , 3021. I. Shiina, H. Oshiumi, M. Hashizume, Y. Yamai, R. Ibuka, . 2004, 45, 543. I. Shiina, M. Kubota, H. Oshiumi, M. Hashizume, . 2004, , 1822. I. Shiina, . 2007, , 239. Tokyo Kasei Kogyo Co., Ltd., Jpn. Kokai Tokkyo Koho 2003 335731, 2003.

Materials Chemistry

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

43

Carbonyl Olefination

Synthetic Organic Chemistry

Carbonyl Olefination

Materials Chemistry

Carbonyl olefination is one of the most fundamental conversions in organic synthesis and a variety of synthetic methods have been developed. Particularly, synthetic methods focused on the chemical properties of heavy-atoms such as phosphorus, silicon and sulfur atoms had long been studied. One of them, the Wittig reaction is the representative carbonyl olefination reaction. Other similar reactions, the silicon-mediated Peterson olefination and two sulfur-based“Julia”carbonyl olefinations named the JuliaLythgoe olefination and the Julia‐Kocienski olefination are also useful olefinating methods. Among them, as the Wittig and Horner-Emmons reactions are the most general carbonyl olefinations, a number of improved synthetic applications have also been investigated. Some of them allow providing easer work-up procedures and increasing the stereoselectivity of the double bond of olefins. They are even now widely used for this transformation. O R1

R3

Olefinating Reagent

R1

R2

Aldehyde, Ketone Wittig Reaction

Horner-Emmons Reaction

R3 R4

Peterson Reaction

R3 R4

PR3

R4 R2 Julia Reaction

R3 R4

POR2

R3 SiR3

R4

/ (Na/Hg)

SO2Ar

Reagents for carbonyl olefination

In the 1990s, organotitanium species-promoted carbonyl olefinations had been studied and various successful methods were reported. The biggest advantage of the use of organotitanium species in carbonyl olefination is that not only aldehydes and ketones, but also esters and lactones can be transformed to the corresponding olefins. Furthermore, the basicities of the organotitanium species are weaker compared to that of Wittig type bases and these chemical properties enable easily enolizable substrates to be used in carbonyl olefinations and to produce the desired olefins with high yields. Tebbe Reagent / Petasis Reagent

O R1

R1

Cp2Ti=CH2

R2

R2

Aldehyde, Ketone Ester, Lactone, Thiolester, Amide

Tebbe Reagent :

Ti

CH2

Cl

Al

CH3 CH3

Petasis Reagent :

[C1411]

CH3 Ti

CH3

[D4100]

Titanium-mediated Methylenating Reagents

A1305

A1439

A1007

O

O

Wittig Reaction

P CH2

C CH3 Cl

44

P CH

C CH3

P CH2CH CH2 Br

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Carbonyl Olefination

A1012

A0862

P

B0824

(CH2)4CH3

Cl

P CH2

B1206

B3928

Cl

B0970

O

P CH2CH2CH2Br

C1061

P

P

(CH2)3CH3

(CH2)4 C OH

Cl

C1378

D2907

Materials Chemistry

C1739

CH2

P

Br

Br

Br

C1286

Cl

O

P CH2 C O C CH3

Br

C1759

CH3 CH3

C1009

Br

Br Br

B1208

P CH2Br

P CH2

Synthetic Organic Chemistry

P CH2CH CH2

B2025

Cl

P CH2Cl

Cl

P CH2CH

P

CH

CH2CN

P

Cl

P CH2

Br

Cl

Br

D4072

Cl

D1654

D1655

D2056

OCH3 P CH2

P CH2CH2N

OCH3

Br

O

O

CH3

P CH2CH2

P CH2CH2

CH3

E0382

E0549

T1944

O P CH2

Br

C1641

O

P CH2CH3

P CH2 C OCH2CH3

OCH2CH3

Br

O

Br

Br

E0407

O P CH2

O

O

Br

E0421

D2164

P CH2CH3 I

Br

P

CH C OCH2CH3

Br

F0331

H0545

H0540

H1240 HO

O

O

P C C OCH2CH3

P CH2

P

C H

CH3

(CH2)6CH3 Br

P

(CH2)5CH3 Br

P CH2

Cl

I0552

Br

M1326

M0828

M0779

M0253

O P CH(CH3)2 I

P CH2

C OCH3

P CH2OCH3

Br

T1363

P CH3

N0700

N0701

P1182

C OCH3

O P CH2

I

T2718

O P CH

P CH3

Br

Cl

Cl

P

CH2

NO2 Br

P CH2

O

C

O

(CH2)3CH3 CH2 P

(CH2)3CH3

Br

(CH2)3CH3

Br

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

45

Carbonyl Olefination

Synthetic Organic Chemistry

T1458

T1510

T1498

CH3

CH3 CH3

C H

P

CHCN

CH3

CH3

T2565

O P CH

P CH2C C Si CH3 Br

I

T2002

T1958

CH3

P CH2CH2 Si CH3

P CH2OCH2CH2 Si CH3 Cl

T2001

P1438

P1200

T1506

O P CH

P C C O

C

P

CH2 C CH

P CH2CH2CH3 Br

P

(CH2)13CH3

Br

Br

Materials Chemistry

T1644

P CH CH2 Br

46

Product No.

Product Name

A1305 A1439 A1007 A1012 A0862 B2025 B0824 B1206 B1208 B3928 B0970 C1061 C1759 C1009 C1286 C1739 C1378 D2907 D4072 D1654 D1655 D2056 D2164 E0421 E0407 E0382 E0549 T1944 C1641 F0331 H0545 H0540 H1240 I0552 M1326 M0828 M0779 M0253 T1363 N0700

Acetonyltriphenylphosphonium Chloride (Acetylmethylene)triphenylphosphorane Allyltriphenylphosphonium Bromide Allyltriphenylphosphonium Chloride Amyltriphenylphosphonium Bromide Benzyltriphenylphosphonium Bromide Benzyltriphenylphosphonium Chloride (Bromomethyl)triphenylphosphonium Bromide 3-Bromopropyltriphenylphosphonium Bromide (tert-Butoxycarbonylmethyl)triphenylphosphonium Bromide Butyltriphenylphosphonium Bromide 4-(Carboxybutyl)triphenylphosphonium Bromide (2-Chlorobenzyl)triphenylphosphonium Chloride (Chloromethyl)triphenylphosphonium Chloride Cinnamyltriphenylphosphonium Bromide (Cyanomethyl)triphenylphosphonium Chloride Cyclopropyltriphenylphosphonium Bromide (2,4-Dichlorobenzyl)triphenylphosphonium Chloride (3,4-Dimethoxybenzyl)triphenylphosphonium Bromide 2-Dimethylaminoethyltriphenylphosphonium Bromide 2-(1,3-Dioxan-2-yl)ethyltriphenylphosphonium Bromide 2-(1,3-Dioxolan-2-yl)ethyltriphenylphosphonium Bromide (1,3-Dioxolan-2-yl)methyltriphenylphosphonium Bromide 4-Ethoxybenzyltriphenylphosphonium Bromide Ethoxycarbonylmethyl(triphenyl)phosphonium Bromide Ethyltriphenylphosphonium Bromide Ethyltriphenylphosphonium Iodide Ethyl (Triphenylphosphoranylidene)acetate Ethyl 2-(Triphenylphosphoranylidene)propionate (Formylmethyl)triphenylphosphonium Chloride Heptyltriphenylphosphonium Bromide Hexyltriphenylphosphonium Bromide (2-Hydroxybenzyl)triphenylphosphonium Bromide Isopropyltriphenylphosphonium Iodide Methoxycarbonylmethyl(triphenyl)phosphonium Bromide (Methoxymethyl)triphenylphosphonium Chloride Methyltriphenylphosphonium Bromide Methyltriphenylphosphonium Iodide Methyl (Triphenylphosphoranylidene)acetate (1-Naphthylmethyl)triphenylphosphonium Chloride

Unit Size

25g 25g 5g

25g 25g 5g 25g

5g 5g 5g 5g 25g 25g 25g 25g

25g 25g 5g 5g 25g 25g 25g

100g 100g 100g 25g 5g

25g 25g 25g 25g 25g 250g 500g 25g 25g 25g 250g 250g 25g 25g 25g 100g 5g 25g 5g 25g 25g 25g 25g 5g 250g 500g 250g 250g 5g 25g 500g 500g 25g 25g 25g 500g 500g 500g 100g 25g

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Carbonyl Olefination

Product Name

N0701 P1182 T2718 T1458 T1510 T1498 T2001 T1958 T2002 T2565 P1438 P1200 T1506 T1644

(4-Nitrobenzyl)triphenylphosphonium Bromide Phenacyltriphenylphosphonium Bromide Tributyl(1,3-dioxolan-2-ylmethyl)phosphonium Bromide 2-(Trimethylsilyl)ethoxymethyltriphenylphosphonium Chloride (2-Trimethylsilylethyl)triphenylphosphonium Iodide (3-Trimethylsilyl-2-propynyl)triphenylphosphonium Bromide (Triphenylphosphoranylidene)acetaldehyde (Triphenylphosphoranylidene)acetonitrile 2-(Triphenylphosphoranylidene)acetophenone (Triphenylphosphoranylidene)ketene Triphenylpropargylphosphonium Bromide Triphenylpropylphosphonium Bromide Triphenyl(tetradecyl)phosphonium Bromide Triphenylvinylphosphonium Bromide

Unit Size

5g 1g 5g 5g 1g 5g 25g

B2801

B1714 O

OCH2CH3

CH2 P CH3O

Horner-Emmons Reaction

CH3O

OCH2CH3

O

O

OCH2CH3

O CH3CH2O P CH2

CH2

CH3CH2O

O

CH3O

P OCH2CH3

CH3O

OCH2CH3

D3069

B1795

B2814 O

OCH3 HN

CH2 CHCH2 P

OCH2CH3

O

CH3

P CH2 C O C CH3

CH3O CH3O

O

O

P

CH3

B1781

CH2 P

O

OCH2CH3

CH3CH2O

O

OCH3 HN

Boc

D3688 O

O

CH3CH2O

C OCH3

CF3CH2O

C2440

O

P

O

OCH2CH3

O

B4011

O CF3CH2O P CH2

P CH2 C OCH2

CH2 P

B1923

25g 25g 5g 25g 5g 5g 25g 25g 5g 5g 25g 500g 25g 5g

Materials Chemistry

B2815

Synthetic Organic Chemistry

Product No.

Cbz

D4434

OCH2CH3 O

OCH2CH3

O

CH3CH2O P CH2CH2Br

CH3CH2O P CH2 CH3CH2O

Br(CH2)3

CH3CH2O

P OCH2CH3 OCH2CH3

Br

C1595

D3335

D4588 O

CH2 P

Cl O CH2

P

D3323

C1430

OCH2CH3 O

OCH2CH3 ClCH2

OCH2CH3 OCH2CH3

O

P OCH2CH3

NC

CH2 P

OCH2CH3

O OCH2CH3 OCH2CH3

CH3CH2O P CH2CN CH3CH2O

Cl

D2423

D4074

E0483

D3324

D3689 O

O CH3CH2O P CH2 CH3CH2O

S

OCH2CH3 OCH2CH3

S

CH2 P

O

O P OCH2CH3 OCH2CH3

CH3CH2O P CH2CH3

O F

CH2 P

CH3CH2O

OCH2CH3

OCH2CH3 OCH2CH3

OCH2CH3

I

D3325

D3326

D4000 O

CH3 CH3

O CH

CH2 P

CH2 P OCH2CH3

D3708 O

OCH2CH3

CH2 P

OCH2CH3

OCH2CH3

OCH3

OCH2CH3 OCH2CH3

D3873 O

CH3

N OCH3

O P

OCH2CH3 OCH2CH3

O CH3OCH2 P OCH2CH3 OCH2CH3

OCH3

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

47

Carbonyl Olefination

Synthetic Organic Chemistry

D3327

D3328 O

O

OCH2CH3

CH2 P

D3336

CH2 P

OCH2CH3 CH3

OCH2CH3

CH2 P

OCH2CH3

O

C CH2 P

OCH2CH3

O N CH2

Materials Chemistry

S S

OCH3

CH3CH2O P CH2SCH3

OCH2CH3

CH3CH2O

N

OCH2CH3

CH2 P OCH2CH3

O0208

OCH3

Cl3C P OCH2CH3 OCH2CH3

D3875 O

O

O

CH3O P CH2

CH3O P CH3

C CH3

Cl Br

O

CH P O

CH3O

CH3O

D3709

O

O

OCH2CH3

OCH2CH3

O P OCH3

P OCH3

D3824

P

M0943

O

O OCH2CH3

D4607

O

D3981

S

P

P1258

P OCH2CH3 OCH2CH3

S

O

O

O

CH3 C CH2

D3992

OCH2CH3

P1193

O

OCH2CH3

OCH2CH3

CH3

D3174

O

M1208

CH3

CH3

D3339

D3827 O

D2547

2

D2548

M1210 O

Cl

O

O CH3

CH P O 2

D2873

O

O

P O

N

O P CH2

2

OCH3

T1582

CH3

O C OCH2CH3

O

O

O P CH2

2

CH3OCH2 P

C OCH2CH3

2

M1319

F0340

D1523

O CH2

O CH3CH2O P CH2

O

P OCH2CH3 OCH2CH3 (CH3)2CHO

C OCH3

(CH3)2CHO

O

CH3CH2O CH2

O

O

P CH2 P

OCH(CH3)2 OCH(CH3)2

CH3CH2O CH3CH2O

P OCH2CH3

O

O

P

O

OCH2CH3 F

O

CH3CH2O P CH2

C OCH2CH3

CH3CH2O

OCH2CH3

T2135

CH3CH2O CH3CH2O

48

D1524

P1265

O

O CH3 O

P CH C OCH2CH3 CH3CH2O P

CH3CH2O

O (CH2)2

C OCH2CH3

O CH3O P CH2

O C OCH3

CH3O

Product No.

Product Name

B2815 B2801 B1923 B1714 B4011 B2814 C2440 D3069 B1795 D3688 B1781 D4434 C1595 D3335

Benzyl Dimethylphosphonoacetate 9,10-Bis(diethylphosphonomethyl)anthracene 4,4'-Bis(diethylphosphonomethyl)biphenyl Bis(2,2,2-trifluoroethyl) (Methoxycarbonylmethyl)-phosphonate N-(tert-Butoxycarbonyl)-2-phosphonoglycine Trimethyl Ester tert-Butyl Diethylphosphonoacetate N-Carbobenzoxy-2-phosphonoglycine Trimethyl Ester Diethyl Allylphosphonate Diethyl Benzylphosphonate Diethyl (4-Bromobenzyl)phosphonate Diethyl 2-Bromoethylphosphonate Diethyl (3-Bromopropyl)phosphonate Diethyl (3-Chlorobenzyl)phosphonate Diethyl (4-Chlorobenzyl)phosphonate

Unit Size

1g

1g 1g 1g 5g 1g 1g 1g 1g 5g 5g 1g 1g 5g

5g 5g 5g 25g 5g 5g 5g 5g 25g 25g 25g 5g 5g 25g

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Carbonyl Olefination

Diethyl (Chloromethyl)phosphonate Diethyl (4-Cyanobenzyl)phosphonate Diethyl Cyanomethylphosphonate Diethyl 2,2-Diethoxyethylphosphonate Diethyl (1,3-Dithian-2-yl)phosphonate Diethyl Ethylphosphonate Diethyl (4-Fluorobenzyl)phosphonate Diethyl (4-Iodobenzyl)phosphonate Diethyl (4-Isopropylbenzyl)phosphonate Diethyl (3-Methoxybenzyl)phosphonate Diethyl (4-Methoxybenzyl)phosphonate Diethyl (N-Methoxy-N-methylcarbamoylmethyl)phosphonate Diethyl (Methoxymethyl)phosphonate Diethyl (2-Methylbenzyl)phosphonate Diethyl (3-Methylbenzyl)phosphonate Diethyl (4-Methylbenzyl)phosphonate Diethyl Methylphosphonate Diethyl (Methylthiomethyl)phosphonate Diethyl (2-Oxo-2-phenylethyl)phosphonate Diethyl (2-Oxopropyl)phosphonate Diethyl (Phthalimidomethyl)phosphonate Diethyl 1-Pyrrolidinemethylphosphonate Diethyl (Trichloromethyl)phosphonate Dimethyl 1,3-Benzodithiol-2-ylphosphonate Dimethyl 2-(1,3-Dithiole)phosphonate Dimethyl Methylphosphonate Dimethyl (2-Oxopropyl)phosphonate Diphenyl 4-Bromo-α-chlorobenzylphosphonate Diphenyl α-Chlorobenzylphosphonate Diphenyl (N-Methoxy-N-methylcarbamoylmethyl)phosphonate Ethyl Diphenylphosphonoacetate Ethyl Di-o-tolylphosphonoacetate Methoxymethyl(diphenyl)phosphine Oxide Methyl Diethylphosphonoacetate Tetraethyl p-Xylylenediphosphonate Tetraisopropyl Methylenediphosphonate Triethyl 2-Fluoro-2-phosphonoacetate Triethyl Phosphonoacetate Triethyl 2-Phosphonopropionate Triethyl 3-Phosphonopropionate Trimethyl Phosphonoacetate

Unit Size

D4100

Organotitanium Reagents

CH3 Ti

1g 5g 5g 5g

5g 5g 5g 5g 1g 5g 5g 5g 5g 5g 5g 1g 5g 5g 5g 1g 25g 5g 5g 1g 1g 1g

25g

1g 100g 25g 25g

C1411

CH3

5g

5g 5g 25g

5g 25g 25g 25g 5g 25g 25g 25g 5g 25g 25g 5g 25g 25g 25g 25g 25g 25g 5g 25g 25g 5g 25g 1g 5g 500g 25g 25g 5g 5g 5g 1g 25g 25g 100g 25g 5g 500g 25g 250g 250g

Materials Chemistry

Product Name

D4588 D3323 C1430 D2423 D4074 E0483 D3324 D3689 D3325 D3326 D4000 D3708 D3873 D3327 D3328 D3336 D3827 M1208 D3339 D3174 P1193 P1258 D4607 D3992 D3981 M0943 O0208 D3875 D3824 D3709 D2547 D2548 M1210 D2873 T1582 M1319 F0340 D1523 T2135 D1524 P1265

Synthetic Organic Chemistry

Product No.

T2052

Ti

Cl

Al

CH3 CH3

TiCl4

T0616

Cl

Ti

Cl

Product No.

Product Name

D4100 C1411 T2052 T0616

Dimethyltitanocene (5% in Tetrahydrofuran/Toluene) Tebbe Reagent (ca. 0.5mol/L in Toluene) Titanium(IV) Chloride (14% in Dichloromethane, ca. 1.0mol/L) Titanocene Dichloride

Unit Size 100g 25mL 100mL 500mL 5g 25g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

49

Carbonyl Olefination

Synthetic Organic Chemistry

B0041

B1444

B0527

SH

Others

SCH2S

B0396

D0184

D0192

D1106

Materials Chemistry

D0610

CH3

Cl

N

CH3

Cl CH3

C CH3 Cl

CH3 N

CH3

CH3

50

O

T0430 CH3

CH3

CH3

D0400

CH3CH2 C CH3

CH2Br2

Br

T0147

CH2I2

.

Cl

Br Li

CH3

BF3

O CH3

O

Product No.

Product Name

B0041 B1444 B0527 B0396 D0184 D0192 D1106 D0400 D0610 T0147 T0430

Benzenethiol Bis(phenylthio)methane Boron Trifluoride - Ethyl Ether Complex Butyllithium (ca. 15% in Hexane, ca. 1.6mol/L) 1,1-Dibromoethane (stabilized with Copper chip) Dibromomethane 2,2-Dichlorobutane 2,2-Dichloropropane Diiodomethane (stabilized with Copper chip) N,N,N ',N '-Tetramethylethylenediamine Triethyl Phosphite

P

O

CH3

Unit Size 25mL 500mL 5g 25g 25mL 100mL 500mL 100mL 500mL 5g 25g 500g 10mL 10mL 25g 100g 500g 25mL 500mL 25mL 500mL

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Carbonyl Olefination

Synthetic Organic Chemistry

-Selective Horner-Emmons Reagent

ArO ArO R CHO Reagent

Materials Chemistry

Horner-Emmons reagents are efficient olefinating reagents for the preparation of α,β-unsaturated esters. Generally, their reaction with aldehydes affords the -isomer of the related olefins preferentially. So, to obtain the -isomer selectively, it is required to investigate the reaction conditions and other effective olefinating reagants. Ando had studied the -preferential Horner-Emmons reaction on the basis of detailed analysis of its reaction mechanism, and resultantly it was found that the -isomer of α,β-unsaturated esters was given with high stereoselectively by use of ethyl (diaryl)phosphonoacetates as olefinating reagents.1) In this synthetic method, quaternary ammonium hydroxides stable to water are available as a base, and it doesn’ t require any special experimental-equipment/-technique. In addition, this method gives -α,β-unsaturated esters with extremely high stereoelectivity, so ethyl (diaryl)phosphonoacetates are the practical Horner-Emmons reagents. O P CH2CO2Et , Triton ® B

D2547 or D2548

R CO2Et

o

THF, -78 C Ar

D2547

Ph

D2548

o-Tolyl

R

Yield (%)

Ph

98

93:7

C7H15

100

90:10

Ph

100

96:4

C7H15

97

94:6

n

n

Product No.

Product Name

D2547 D2548

Ethyl Diphenylphosphonoacetate Ethyl Di-o-tolylphosphonoacetate

(Z :E)

Unit Size

1g

5g 1g

References 1) a) K. Ando, . 1995, , 4105. b) K. Ando, . 1997, , 1934. c) K. Ando, T. Oishi, M. Hirama, H. Ohno, T. Ibuka,

. 2000,

, 4745.

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

51

Cross-coupling Reaction Using Transition Metal Catalysts

Synthetic Organic Chemistry

Cross-coupling Reaction Using Transition Metal Catalysts

Materials Chemistry

Cross-coupling reactions using late transition metal catalysts represented by nickel and palladium metals have been widely used for introducing various functional groups into unsaturated substances such as aromatic rings, alkenes, alkynes and so on. In these reactions, carbon-carbon bond forming reactions can be performed by the combination of electrophilic carbon species of aryl/vinyl halides and organometallic agents of Grignard reagents and organoboron compounds. Also, the use of nucleophilic hetero atoms such as phenols and amines is efficient to form carbon-hetero atom bonds. By the development of these synthetic methods, substitution reactions to sp2 carbon and sp carbon are easily accomplished while it had been difficult to perform these transformations by classical synthetic reactions without using metal catalysts.

R

X +

catalyst

M R' or

HYR'n

R R' or

(-M+X- or HX)

R

YR'n

catalyst = Pd, Ni, Cu, Fe etc. R = Ar, alkenyl, Het X = I, Br, OTf, Cl etc. M = Mg, Zn, Sn, B, Si etc. Y = N, O, P, S etc.

Recently, transition metal mediated cross-coupling reactions have been widely used as useful synthetic tools and applied to the synthesis of various functional molecules such as bioactive compounds and biaryls for liquid crystal materials. As a feature of these transformations, it is found that there are many name reactions for each kind of nucleophile used for coupling reactions. And then in 2010, for making a great contribution to develop the metal-based cross-coupling reactions, Richard F. Heck, Ei-ichi Negishi and Akira Suzuki jointly received the Nobel Prize in chemistry, verifying the usefulness of the transition metal mediated cross-coupling reactions. The following shows the synthetic properties of palladium/nickel catalyzed cross-coupling reactions commonly used with the chemical equations. R'-M

R-MII-R'

(-M+X-) Transmetalation

R

Reductive elimination

Catalyst regeneration

Kosugi-Migita-Stille cross-coupling

Miyaura-Ishiyama cross-coupling

Suzuki-Miyaura cross-coupling

M= Pd, Ni L= PR3 etc.

R-MII-X

+

Kumada-Tamao-Corriu cross-coupling Hiyama cross-coupling Sonogashira-Hagiwara cross-coupling Negishi cross-coupling

X Oxidative addition

M(0)Ln

M(0)Ln

R R'

M(0)Ln

RnY-H

+ Ar-MII-Nu R Nu Base (-HX) Reductive elimination Nucleophilic substitution Buchwald-Hartwig cross-coupling Y= N, O, P, S etc.

Catalyst regeneration

Tsuji-Trost allylation

H

H

R'

R'

R

Insertion

MIIX

β-Hydride elimination

R'

R

O

Insertion

52

R

O

R'-M or Nu-H

MIIX

R

H-MII-X

Reductive elimination

Mizoroki-Heck reaction

CO

+

R'

Transmetalation Nucleophilic substitution & Carbonylation Reductive elimination

+

(-HX)

M(0)Ln Catalyst regeneration

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Cross-coupling Reaction Using Transition Metal Catalysts

Cross-coupling reactions using palladium/Nickel catalysts

Chemical properties for Ni/Pd catalysts

X: I > Br ≈ OTf > Cl >> F

Br

OTf

High reactivity but low stability

Ni

Reactive without phosphine ligands at room temperature

I

Synthetic Organic Chemistry

Chemical properties and reactivities for organic halides (R-X)

Inexpensive and easy to remove

In many cases heating is required for the reactions to proceed.

Chemically stable and easy to handle

Formation of cationic complexes is unfavorable for metal exchange reactions.

Little by-product

Pd

Effective to add some salts like LiCl for the reactions to proceed

Expensive and hard to remove

Only in a special case will the reactions proceed.

Cl

Use of highly active catalysts

R

The order of the reactivity as follows: Electron-withdrawing group > electron-donating group

High electron-donation

Improves oxidative addition

Electron-withdrawing group is effective for oxidative addition.

High bulky ligand

Improves reductive elimination

Materials Chemistry

Effect of ligand (L) for reactivity

Use of heteroaromatic chlorides (R = heteroaromatic rings)

As a means for preventing deactivation of catalysts, it is effective to carry out the reaction under inert gas (argon, nitrogen) conditions. In addition, performing degasification of the solvent before the reaction is more effective.

The late transition metal catalyzed cross-coupling reactions are collected based on the reaction modes and show as general synthetic schemes as follows. Cross-coupling reactions

the transmetalation Hiyama cross-coupling

Kumada-Tamao-Corriu cross-coupling R

X + R'

Ni(0) cat.

MgX

X + R'

X + R'

Pd(0) cat.

ZnX

Ar X

Kosugi-Migita-Stille cross-coupling X + R'

Pd(0) cat.

SnR''3

R R'

X + R'

B(OR'')2

R'

+

Pd(0) cat. Cu(I) cat.

+

X

Pd(0) cat.

(RO)2B B(OR)2

Pd(0) cat.

Ar

R'

Base

Miyaura-Ishiyama Borylation Ar

Suzuki-Miyaura cross-coupling R

R R'

Sonogashira-Hagiwara cross-coupling

R R'

(R'–AlR2 and R'–ZrCp2Cl can be also used.)

R

Pd(0) cat.

SiR''3

(SiR''3=Si(OR)3, SiR3-nFn, etc.) (SiR''3=Si(OH)Me2: Hiyama-Denmark coupling)

Negishi cross-coupling R

R

R R'

Base

Ar B(OR)2

R R'

Base

Cross-coupling reactions forming carbon-hetero atom bonds Chan-Lam-Evans cross-coupling

Buchwald-Hartwig cross-coupling Ar

X + H YR'n

Pd(0) cat. Base

Y= N, O

Ar

YR'n

Y= N, O, S

Cross-coupling reactions

X +

Ar

Base, O2

YR'n

Carbonylation via CO insertion

Pd(0) cat.

R'

Cu(OAc)2

the insertion

Mizoroki-Heck reaction R

Ar B(OH)2 + H YR'n

Base

R

R'

Nu H R

X +

R'

or or

H

M

O Pd(0) cat. CO

R

Nu or R' or H

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

53

Cross-coupling Reaction Using Transition Metal Catalysts

Synthetic Organic Chemistry

Cross-coupling reactions

the oxidative addition of thiolesters Liebeskind-Srogl cross-coupling

Fukuyama cross-coupling O R

+ R' ZnX

O

Pd(0) cat.

R

SEt

O R'

R

SEt

+ R' B(OH)2

Pd(0) cat. CuTc

O R

R'

Cross-coupling reactions forming carbon sp3 ‒ carbon sp3 bonds Kochi-Furstner cross-coupling R

X + R'

MgX

Fe(acac)3 THF-NMP

R R'

Materials Chemistry

Palladium Catalysts The study of coupling reactions using organopalladium complexes has been advanced as well as that using organonickel complexes. Generally, the reactivity of organopalladium complexes is lower compared with organonickel complexes. However, they have higher chemical stability for oxidations and this makes them easy to use. Therefore, palladium complexes are most commonly used for cross-coupling reactions. (1) Palladium complexes generally used in cross coupling reactions Palladium-phosphine complexes are well used in cross-coupling reactions and commercially available. Pd(PPh3)4 and PdCl2(PPh3)2 are used without any treatment. Also, palladium catalysts are used prepared from the precursors such as Pd(OAc)2 and Pd2(dba)3・CHCl3, with appropriate amounts of phosphines. When using divalent palladium complexes such as Pd(OAc)2, once they are reduced to zerovalent palladium species by some organometallic reagents, phosphines and amines, then their catalytic reactions can start. Palladium-phosphine complexes: Pd(0): Pd(PPh3)4, Pd[P(t-Bu)3]2 etc. Pd(II): PdCl2(PPh3)2, PdCl2[(o-tolyl)3P]2, PdCl2(dppf), PdCl2(dppe), PdCl2(dppp), etc. Precurcors of palladium catalysts: Pd(0): Pd2(dba)3·CHCl3, Pd(dba)2 etc. Pd(II): Pd(OAc)2, PdCl2(CH3CN)2, PdCl2(PhCN)2, [PdCl(allyl)]2, Na2PdCl4, PdCl2 etc.

(2) Higher activity palladium catalysts Generally, cross coupling reactions are promoted by using electron-rich and sterically hindered ligands. For example, palladium catalysts when coordinated by tertiary alkyl phosphines such as the -butyl group, cyclohexyl group and so on are used, show high catalytic activities in cross-coupling reactions. They are effective to use when low reactive aryl chlorides or sterically hindered aromatic halides are employed as reagents. The monomer state of sterically hindered alkyl phosphines is chemically unstable, but they are stabilized by coordinating them with palladium complexes. Me

CN Cl MeO

OMe

CN Me

2% Pd[P(t-Bu)3]2 [B3161]

+ ClZn

THF/NMP, 100 °C Me

MeO

Me OMe 76%

Recently, -heterocarbene (NHC) ligands have been used for cross-coupling reactions because they activate palladium catalysts more effectively than tertiary alkyl phosphines. Palladium-NHC complexes show not only high activity but also high structual stability. In addition, they keep their complex formation without decomposition even after work-up, which is an advantage because it makes removing these complexes easy. 54

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Cross-coupling Reaction Using Transition Metal Catalysts

Synthetic Organic Chemistry

(3) Palladacycle catalysts In some cases the active palladium species can’ t be efficiently prepared by the combination of palladium complexes and ligands. To solve this problem, palladacycle catalysts have been developed and used for more efficient preparation of active palladium species. As a property, they easily release the coordinated ligand with treatment of some bases, and afford the related zero-valent active palladium species. On the other hand, they form structurally stable complexes caused by their cyclic structures constructed of the ligand with intramolecular coordinating ability and the palladium species. In addition, their catalytic ability is improved by the addition of bases and they show high turnover frequency. Cl Cl

base

D PdII

L

X

reductive elimination

HO N

Cl Pd Pd Cl

L

Pd0

active Pd species

C(CH3)3

Cl

D

Cl

Najera catalyst I [C2734]

[D3806]

A1479

B2029

CH2

Palladium Catalysts

B1668

HC

Pd CN

Cl Cl

Fe

Ph

Ph3P

B1676

Pd

2

B2031

Fe

Pd

Ph

B2055

Ph Ph P Cl Pd P Cl Ph Ph

PdCl2 P C(CH ) 3 3 C(CH3)3

B2161

B2018 CH3

Ph Ph P Cl Pd Cl P

. CH2Cl2

(CH3CN)2PdCl2

CH2

C(CH3)3 P C(CH3)3

B2192 Ph P Ph PdCl2 P Ph

Cl

B3160

2

Ph

B3161

CH2

CH CH C CH CH

P Ph

B2064 Ph Ph P Pd P Ph Ph

CH

O

Pd

Cl

B2016

Ph3P

CH2 Pd

B1374 Ph Ph P

Cl

Cl

CH2

B3224 CN

Cl

Pd

Materials Chemistry

palladacycle (stable complex)

NH Pd C(CH3)3 Cl P C(CH3)3

N OH

CH3Ph2P Pd CH3Ph2P

O

Cl

Pd

Cl

O CH3

Ph

B2042

B1667

2

B2026 CH3

t-Bu3P

O

P Pd

3

t-Bu3P

Cl

Ph3P

Cl

Ph3P

Pd P

Pd

O C CH3

Ph3P

O C CH3

Ph3P

Pd

P

Cl

3

CH3

Cl

O

3

Pd

Cl Cl

P 3

C2734

D2604

D3806 Cl Cl

NH2

Pd C(CH3)3 Cl P C(CH3)3

Pd

P1785 P1491 P1490

A1424

HO

Cl Pd

Cl

N OH

C(CH3)3

Cl Pd Cl

N

O Pd

CH3 C O

Pd2 2

Cl Cl

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

55

Cross-coupling Reaction Using Transition Metal Catalysts

Synthetic Organic Chemistry

P2106

P1489

P2017

PdCl2

[Pd(CH3COO)2]3

P1425

P1944

P1528

CH2 HC

Pd

Cl

CH3 NH

O

P

PdCl2

C2372

2

20

Pd / (PSi-Al2O3)

N

N

i-Pr

i-Pr

Materials Chemistry

CH3O

2

i-Pr

i-Pr N

i-Pr CH3O

N

i-Pr

i-Pr

Pd

CH3O

Cl

N

i-Pr

CH3 CH3

Cl

O

HN

N

T1350

Pd2

i-Pr

N

Pd

Cl

N

S0540 i-Pr

C O

C2387 i-Pr

CH3 CH3

C2407

CF3

C2406 i-Pr

Pd

n

Pd(OH)2

CH CH2

i-Pr CH3

O

CH

Cl

Pd CH

P1870

CH3

T2184

i-Pr N

N

i-Pr

i-Pr

Pd HN

O

Na2PdCl4

Cl

P 3

Pd 4

Pd2

CH CH C CH CH 3

O CH3

56

Product No.

Product Name

A1479 B2029 B1676 B1668 B3224 B1374 B3160 B2031 B2016 B2064 B2192 B2161 B2018 B3161 B2055 B2042 B1667 B2026 C2734 D2604 D3806 P1785 P1491 P1490 A1424 P2106 P1430

Allylpalladium(II) Chloride Dimer Benzylbis(triphenylphosphine)palladium(II) Chloride Bis(acetonitrile)palladium(II) Dichloride Bis(benzonitrile)palladium(II) Dichloride Bis[1,2-bis(diphenylphosphino)ethane]palladium(0) Bis(dibenzylideneacetone)palladium(0) [1,1'-Bis(di-tert-butylphosphino)ferrocene]palladium(II) Dichloride [1,4-Bis(diphenylphosphino)butane]palladium(II) Dichloride [1,2-Bis(diphenylphosphino)ethane]palladium(II) Dichloride [1,1'-Bis(diphenylphosphino)ferrocene]palladium(II) Dichloride Dichloromethane Adduct [1,3-Bis(diphenylphosphino)propane]palladium(II) Dichloride Bis(methyldiphenylphosphine)palladium(II) Dichloride Bis(2,4-pentanedionato)palladium(II) Bis(tri-tert-butylphosphine)palladium(0) Bis(tricyclohexylphosphine)palladium(II) Dichloride Bis(triphenylphosphine)palladium(II) Diacetate Bis(triphenylphosphine)palladium(II) Dichloride Bis(tri-o-tolylphosphine)palladium(II) Dichloride Chloro[(tri-tert-butylphosphine)-2-(2-aminobiphenyl)]palladium(II) Dichloro(1,5-cyclooctadiene)palladium(II) Najera Catalyst I Palladium 10% on Carbon (wetted with ca. 55% Water) [Useful catalyst for coupling reaction, etc.] Palladium 10% on Carbon (wetted with ca. 55% Water) Palladium 5% on Carbon (wetted with ca. 55% Water) Palladium(II) Acetate Palladium(II) Acetate Trimer Palladium Catalyst Set (includes useful 7 Palladium catalysts)

Unit Size 500mg 100mg 1g 1g 1g 1g 1g 1g 1g 1g 5g 1g 1g 1g 250mg 1g 1g 1g 5g 1g 1g 250mg 5g 5g 5g 1g 1g

1g 1g 5g 5g 5g 5g 5g 5g 5g 25g 5g 5g 5g 1g 5g 5g 25g 5g 1g 5g 1g 25g 25g 25g 5g 5g

Palladium(II) Acetate / Allylpalladium(II) Chloride Dimer / Bis(benzonitrile)palladium(II) Dichloride / Bis(dibenzylideneacetone)palladium(0) / [1,1'-Bis(diphenylphosphino)ferrocene]palladium(II) Dichloride Dichloromethane Adduct / Bis(triphenylphosphine)palladium(II) Dichloride / Tetrakis(triphenylphosphine)palladium(0)

P1489 P2017 P1528 P1870 P1425

Palladium(II) Chloride Palladium(II)(π-cinnamyl) Chloride Dimer Palladium Hydroxide 20% on Carbon (wetted with ca. 50% Water) Palladium(II) Trifluoroacetate Poly[N-isopropylacrylamide-co-4-(diphenylphosphino)styrene] Palladium(II) Dichloride

P1944 C2372 C2406 C2387 C2407 C0540

Poly(methylphenyl)silane supported Palladium/Alumina Hybrid Catalyst [=Pd / (PSi-Al2O3)] SingaCycleTM-A1 (This product is unavailable in the U.S.) SingaCycleTM-A2 (This product is unavailable in the U.S.) SingaCycleTM-A3 (This product is unavailable in the U.S.) SingaCycleTM-A4 (This product is unavailable in the U.S.) Sodium Tetrachloropalladate(II)

1set 5g 200mg 10g 50g 1g 5g 1g

(ratio, acrylamide:phosphine=20:2)

200mg 200mg 200mg 200mg

100mg 1g 1g 1g 1g 1g 1g

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Cross-coupling Reaction Using Transition Metal Catalysts

Product Name

T1350 T2184

Tetrakis(triphenylphosphine)palladium(0) Tris(dibenzylideneacetone)dipalladium(0)

Unit Size 1g

5g 1g

Synthetic Organic Chemistry

Product No.

25g 5g

Nickel Catalysts

B(OH)2 +

Materials Chemistry

Nickel catalysts are routinely used for cross-coupling reactions as well as palladium catalysts. In 1972, Kumada and Tamao had reported that nickel catalysts promoted cross-coupling reactions of Grignard reagents with aryl halides or vinyl halides with the proposal their catalytic cycle. The result of this research has contributed to further development of cross coupling reactions.1) Nickel catalysts are generally inexpensive and show high activities even when using low reactive substrates in cross-coupling reactions. For example, in the presence of butyl lithium, zinc metal or phosphines as a co-reductant, NiCl2(dppf) catalyzed cross-coupling reactions of aryl chlorides/mesylates with aryl borates successfully proceeding to afford the desired biaryls in good yields.2) Recently, it has been reported that -heterocyclic carbene (NHC) ‒ nickel complexes show high catalytic activity in cross-coupling reactions. cat. NiCl2(dppf), BuLi [B2226]

Cl

K3PO4, dioxane, 80 °C OMe

OMe Y. 94 % [when Pd(PPh3)4 Y. < 1%]

H3C

Ph

O O H3C Ni(acac)2 [N0096]

Ni source

Ni xH2O

Ni P Ph

Ph

Ph P

Ph

[B2225]

Cl

Ni

Cl

P Ph

Ph

Ph P

Cl Cl

Ni

Fe P

Ph

[B1313]

Ph P

Ph [B2226]

Ni-phosphine complexes

Ph

i-Pr Cl Cl

i-Pr N

N

i-Pr i-Pr Cl Ni Cl PPh3 [B3235]

Ni-NHC complex

On the other hand, similar to iron and cobalt catalysts, nickel catalysts are used for the cross coupling reactions of alkyl halides with organometallic species such as organomagnesium, organozinc and organoboric acid compounds. This synthetic means is effective for producing the carbon sp3 ‒ carbon sp3 bond. In this reaction, phosphine ligands are less effective and an optimization of the reaction conditions suitable for each substrate was investigated. In a case using primary alkyl halides as a reactant, the coupling reactions are accelerated by using NMP as a solvent and addition of alkenes with electron-withdrawing groups. It is also effective to add butadienes as additives because the reactivity of the coupling reactions improves through the formation of nickel - bis-allyl complexes. The proceeding of cross-coupling reactions with secondary alkyl halides is harder relative to primary alkyl halides, so pyridyl-type chelate ligands such as phenanthrolines, Pybox and diamines are used for promoting those reactions. This has been applied to asymmetric reactions and natural products synthesis.3)

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

57

Cross-coupling Reaction Using Transition Metal Catalysts

Synthetic Organic Chemistry

Cross coupling of primary alkyl halides

n-alkyl

X +

R MX

cat. Ni(acac)2 or NiX2 additive

Cross coupling of secondary alkyl halides

n-alkyl

X + R'

R

X= I, Br R= n-alkyl, s-alkyl, benzyl, aryl M= Zn

O

Me etc.

etc.

(base or additive)

R2

N

N R

R'

ZnX

B3235

Materials Chemistry

R1 R'

X= I, Br, MY= ZnX, B(OH)2, BBN, SiF3, Si(OMe)3 etc. R'= alkyl, aryl, alkenyl Ligand: Ph Ph Ar O O N

M= Mg

F

MY

R2

THF/NMP

additive:

cat. NiX2 cat. Ligand

R1

R

N

N

Ar Ar

B(OH)2 SiF3

B2225

Me

Ar

etc.

NH HN Me R' BBN R' Si(OMe)3

B2226

(CH3)2CH

Ph N

Nickel Catalysts (CH3)2CH

B1313

N0096 Ph

Ni

Ni Cl

P Ph

P

O

Cl

3

O CH3

Ph

Ph

Fe

Cl

Ph

Ph

S0487

Cl

Ph3P

Cl

Ph3P

Ni P

2

Ni

P

Cl

B1571

CH3

Ph P

B3534

Ph P Ph NiCl2 P Ph

Ph P

CH(CH3)2 N Ni Cl PPh3 Cl CH(CH3)2

Ni

Cl Cl

Ni

3

Product No.

Product Name

B3235 B2225 B2226 B1313 N0096 B3534 B1571 S0487

[1,3-Bis(2,6-diisopropylphenyl)imidazol-2-ylidene]triphenylphosphine Nickel(II) Dichloride 200mg [1,2-Bis(diphenylphosphino)ethane]nickel(II) Dichloride 1g 5g [1,1'-Bis(diphenylphosphino)ferrocene]nickel(II) Dichloride 1g [1,3-Bis(diphenylphosphino)propane]nickel(II) Dichloride 5g 25g Bis(2,4-pentanedionato)nickel(II) Hydrate Bis(tricyclohexylphosphine)nickel(II) Dichloride 1g Bis(triphenylphosphine)nickel(II) Dichloride 10g Skeletal Nickel Catalyst slurry in Water [Active catalyst for Hydrogenation]

Unit Size 1g 25g 5g 25g 500g 5g 100g 50g

References 1) K. Tamao, K. Sumitani, M. Kumada, . 1972, , 4374. 2) a) V. Percec, J.-Y. Bae, D. H. Hill, . 1995, , 1060. b) S. Saito, M. Sakai, N. Miyaura, . 1996, , 2993. c) S. Saito, S. Oh-tani, N. Miyaura, . 1997, , 8024. d) A. F. Indolese, . 1997, , 3513. 2000, e) K. Inada, N. Miyaura, , 8657. 3) Review a) M. R. Netherton, G. C. Fu, . 2004, , 1525. b) F. Glorius, . 2008, , 8347. c) A. Rudolph, M. Lautens, . 2009, , 2656.

58

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Cross-coupling Reaction Using Transition Metal Catalysts

Synthetic Organic Chemistry

Iron Catalysts Including palladium catalysts, which are frequently used for the Suzuki-Miyaura coupling reaction, transition metal catalysts, such as nickel, copper, or rhodium, have been widely used for organic synthesis. However, the percentages of these metals in the earth’ s crust are extremely small, and their prices are rather expensive.1) On the other hand, iron is abundant and less expensive, therefore, more and more chemists have focused their attention to organic synthesis using iron compounds as a catalyst. 2) For instance, with regards to the reactions of Grignard reagents with alkyl bromides, Hayashi and 3) Chai have reported the synthetic methods using Fe(acac)3 as a catalyst, Fe(OAc)2 as a catalyst and Xantphos as a ligand, respectively, by which the desired coupling products can be obtained in good yields. (CH2)5CH3 Br

Fe(acac)3 (5 mol%) [I0079] Et2O, reflux, 0.5 h

Materials Chemistry

MgBr

+

(CH2)5CH3 Y. 73%

8

Br

MgBr

+

Fe(OAc)2 [I0765] (3 mol%)

Xantphos [B2709]

O

PPh2 (6 mol%)

PPh2

8

Et2O, rt, 15 min

Y. 64%

Furthermore, Nakamura have reported the method using the -heterocyclic carbene generated from SIPr・HCl, which suppresses the generation of the homo-coupling products, thereby leading to an excellent yield of the desired product.4) Cl

iPr

N iPr

Cl

Pr

iPr

SIPr HCl (15 mol%) [B3157]

FeF3 3H2O (5 mol%)

+ BrMg

i

N +

THF, 60 °C, 24 h Y. 98%

Thus, synthetic technologies using iron catalysts are being actively developed. It can be expected that iron catalysts will exhibit their own catalytic properties in addition to replacing other metal catalysts in the near future.

D2571

I0765

T1686 Ph

N

Iron Catalysts

N Fe

O

O

O CH3 C O

O

Fe 2

Fe

2

O Ph

H0555

I0079

T0750 CH3

CF3 O

CF3 O

O Fe

Fe

Fe

O CF3

O

O 3

3

CH3

3

CH3

3

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

59

Synthetic Organic Chemistry

Cross-coupling Reaction Using Transition Metal Catalysts

Product No.

Product Name

D2571 I0765 T1686 H0555 I0079 T0750

N,N '-Bis(salicylidene)ethylenediamine Iron(II) Iron(II) Acetate Tris(dibenzoylmethanato) Iron Tris(hexafluoroacetylacetonato)iron(III) Tris(2,4-pentanedionato)iron(III) Tris(trifluoro-2,4-pentanedionato)iron(III)

Unit Size 5g 5g 5g 25g

100g

25g 25g 25g 1g 500g 5g

References 1) 2) 3) 4)

J. Emsley, in , 3rd ed., Oxford Univ. Press, New York, 1998. 2004, , 1297. T. Nagano, T. Hayashi, 2007, K. G. Dongol, H. Koh, M. Sau, C. L. L. Chai, , 1015. 2007, T. Hatakeyama, M. Nakamura, , 9844.

Materials Chemistry

Copper Catalysts Copper-mediated coupling reactions have been known as a traditional reaction. For instance, homocouplings of aryl halides and alkynes are called the Ullmann reaction and the Glaser coupling respectively, and both of these were discovered over a hundred years ago. Around the same time, carbonheteroatom bond forming reactions such as the Ullmann ether synthesis and the Goldberg amination were also reported. In early studies of these classical copper-mediated coupling reactions, there were a number of disadvantages needing improvement such as use of over stoichiometric amounts of copper reagents, harsh reaction conditions, and low substrate generality. However, copper-mediated coupling reactions can be carried out at a lower cost compared with using palladium catalysts. So, various modified methods have been studied and more practical reactions have been developed. Recent advances in the Ullmann-type reactions using aryl halides have been achieved under milder reaction conditions and reducing the amount of copper catalyst by the choice of suitable solvents, bases, and ligands. Also, investigation of effective ligands for these reactions has been developed and found that the diamine and dicarbonyl compounds effectively play as a ligand in preventing side reactions and deactivating a monovalent copper catalyst. Ullmann-type Coupling Cu(I) source, Ligand Ar

X

Nu

+

Ar

Nu

base, Δ under Ar or N2

X= I, Br

Nu:

Nu:

Ligand O

R

O CO2H

N H

R'

HO

OH

R' R

NH2 H2N

H2N

N

O

etc.

CO2H

CO2H

NHR

HO R

N N

etc.

N

CO2H

etc.

R=H or Me MeO

R HN

HO Ar

etc.

O RHN

Ligand

O

HN

HN

Cu(I) source: CuI, Cu2O, CuBr, (CuOTf)2-C6H6, CuCl etc. Cu(I) complex: CuTC, Cu(MeCN)4PF6 etc. solvent: DMSO, DMF, NMP, dioxane, MeCN, toluene etc. base: K2CO3, K3PO4, Cs2CO3, DIPEA, Et3N etc.

OMe

Salen

N

MeHN

NHMe

N

N

etc.

HS R

HO

OH

etc.

NaI (X= Br)

MeHN

NHMe

For instance, CuTc (copper(I) 2-thiophenecarboxylate) catalyzed the Ullmann coupling and can proceed at room temperature without having to apply heat. CuTc also acts as a co-catalyst of palladium catalyzed reactions. In a case of the Liebeskind-Srogl cross-coupling reaction, CuTc assisted activation of thioesters plays an important role in promoting the coupling reaction.

60

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Cross-coupling Reaction Using Transition Metal Catalysts

Synthetic Organic Chemistry

Liebeskind-Srogl Cross-coupling Reaction O Pd cat. CuTc

O R

SEt

+

R' B(OH)2

S

O

Cu R

R'

O

CuTC [C2312]

Furthermore, the coupling reaction of aryl boronic acids with amines, phenols, and thiols promoted by a divalent copper and an oxygen from the air as a reoxidant, is known as the Chan-Lam-Evans coupling. This is a halogen-free coupling reaction and the stirring efficiency is important for the reaction to proceed due to reoxidizing the copper catalyst by an oxygen in the air. The rate of this reaction is generally slow and requires several days to complete the reaction, while it is carried out at room temperature. Chan-Lam-Evans Coupling B(OH)2 +

Cu(OAc)2, O2 Et3N or Pyr

HYRn Y= N, O, S

Ar

B1513

B3834 B1677

CH3

H N

O

Copper Catalysts

C2422

(CH3)2CH

2

A1540 CH3

N CH3

N

Cl Cl

O Cu N

O

2

C2346

C1952

CH3

N

N N

N H

O

(CH3)2CH

CH(CH3)2 Cu Cl CH(CH3)2

Cu

Cu CH3

C2304

YRn

CH2Cl2, MS 4A r.t.~

C0384

Materials Chemistry

Ar

O

CH3 Cu Cl CH3

CH3

O OCu

CH3 C O

Cu2

CuCN

. H 2O

2

CH3

C2410

C2312

Cu(BF4)2

T1292

Cu

D2542 H3C CH3 N Cu N H3C CH3

O

S

H3C CH3 N Cu O N H H3C CH3 H O

Cu2

S O O

D3891 O

O CF3

O

D4395

T1442

CF3

O

2

T2665

N

.

S OCu

Cu N

2

Cl Cl

T2666

2

2Cl

Li2CuCl4

(CH3CN)4Cu

PF6

Product No.

Product Name

C0384 B1513 B3834 B1677 C2304 C2422

Bis(2,4-pentanedionato)copper(II) Bis(1,3-propanediamine) Copper(II) Dichloride Bis(8-quinolinolato)copper(II) (purified by sublimation) Bis(8-quinolinolato)copper(II) Chloro[1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene]copper(I) Chloro(1,3-dimesitylimidazol-2-ylidene)copper(I)

(CH3CN)4Cu

BF4

Unit Size 25g 1g

200mg 200mg

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

250g 10g 1g 25g 1g 1g

61

Synthetic Organic Chemistry

Cross-coupling Reaction Using Transition Metal Catalysts

Product No.

Product Name

A1540 C2346 C1952 C2410 C2312 T1292 T1442 D3891 D2542 D4395 T2665 T2666

Copper(I) Acetate Copper(II) Acetate Monohydrate Copper(I) Cyanide Copper(II) Tetrafluoroborate (ca. 45% in Water) Copper(I) 2-Thiophenecarboxylate Copper(II) Trifluoromethanesulfonate Copper(I) Trifluoromethanesulfonate Benzene Complex Dichloro(1,10-phenanthroline)copper(II) Di-μ-hydroxo-bis[(N,N,N ',N '-tetramethylethylenediamine)copper(II)] Chloride Dilithium Tetrachlorocopper(II) (ca. 2.5% in Tetrahydrofuran, ca. 0.1mol/L) Tetrakis(acetonitrile)copper(I) Hexafluorophosphate Tetrakis(acetonitrile)copper(I) Tetrafluoroborate

Unit Size 5g 25g 25g 1g 5g 1g 1g 5g 100mL 1g

25g 500g 300g 500g 5g 25g 5g 5g 25g 500mL 5g 5g

References Materials Chemistry

1) Review a) S. V. Ley, A. W. Thomas, . 2003, , 5400. b) G. Evano, N. Blanchard, M. Toumi, . 2008, , 3054. c) S. U. Tekale, V. B. Jadhav, V. P. Pagore, S. S. Kauthale, D. D. Gaikwad, R. P. Pawar, 281.

, 2013,

,

Phosphine Ligands Phosphines are a three-valent phosphorus compound and act as a‘soft’σ-donating ligand with an unshared electron pair. This gives solubilization and stabilization to organometallic complexes by forming complexes with various transition metal species including latter-period transition metals and others, and is also used for controlling the reactivity and selectivity of the transition metal promoted reactions. Electron density and bulkiness of phosphine ligands are greatly related to the reactivity of their forming metal complexes. Generally, the phosphine ligands with high electron density increase the reactivity of oxidative addition from a metal center, and their bulkiness improves the reductive elimination. For example, trialkylphosphines especially -butyl or cyclohexyl group substituted phosphines show the highest electron density while the electron density of triarylphosphines and phosphite are sequentially decreasing. On the other hand, as an index of the bulkiness of phosphine ligands, that of monodentate phosphine ligands shows the cone angle (θ) while bidentate phosphine ligands show the bite angle (ω). As the angle of the phosphine ligands is wider, their steric effect is greater and they are regarded as more bulky phosphine ligands. A monodentate phosphine ligand of tri( -tolyl)phosphine, and bidentate phosphine ligands of 1,1'-bis(diphenylphosphino)ferrocene and Xantphos are known as representative bulky phosphine ligands. R R

Wider

R

P(o-tol)3 P(t-Bu)3 P PCy3 θ PPh3 θ M P(O(o-tol))3 P(n-Bu)3 Cone angle of P(OPh)3 P(OMe)3 monodentate phosphines Narrower (θ)

R

R P

R

ω

Wider

P

M Bite angle of bidentate phosphines (ω)

R

ω

Xantphos DPEphos DPPF DPPB BINAP DPPP DPPE

Narrower

Wider DIOP PPFA BINAP Norphos DIPAMP Chiraphos Narrower

Electron rich and bulky trialkylphosphine ligands such as tributylphosphine and tricyclohexylphosphine are highly effective to use for cross-coupling reactions due to their functionally promoting the process of catalytic cycles, both the oxidative addition and reductive elimination. For instance, aryl chlorides have low reactivity against the oxidative addition of transition metals so it generally doesn’ t proceed. However, successful oxidative addition of them can be accomplished by the use of bulky trialkylphosphine ligands. In this way, trialkylphosphines have excellent chemical properties but they are unstable in air. So, it is required to handle them in a glove box. As an improvement of this disadvantage, the salt of phosphonium borates is used as a precursor of phosphine ligands. These can be treated in air and after neutralization the generated alkylphosphines are available in the reactions. Recently, alkyl group-substituted biarylphosphine ligands with higher activity have been developed and used in cross-coupling reactions. Also, unique phosphine ligands with high electron density but chemically stable in air named BRIDPs® have been developed.2)

62

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Cross-coupling Reaction Using Transition Metal Catalysts Advantages of vBRIDP® Increasing bulkiness

Bulky alkyl groups

Ar

Ar

R'

Ar

Ar

Ar

P R

Ar

Controlling electron density

Synthetic Organic Chemistry

High electron density at C2-carbon

Advantages of cBRIDP®

R' P R R

R

Bulky alkyl groups

Aryl groups located desired positions

*BRIDP® is a registered trademark of TAKASAGO INTERNATIONAL CORPORATION.

PPh2

PPh2

H3C

Me OCH3

Ph2P

CH3

PPh2

PPh2

(R,R)-Norphos [B3449]

(S,S)-Chiraphos [B2704]

O

NMe2 PPh2

PCH2CH2P

PPh2

PPh2

Fe

H3CO

PPh2

O

Materials Chemistry

Generally, phosphines are widely used as a ligand for nickel or palladium catalysts in crosscoupling reactions. They are also effective ligands for rhodium, iridium and gold catalysts and used in catalytic reactions such as hydrogenation and cyclization reactions. Furthermore, a number of optically active phosphine ligands with chiral carbon centers, axial chirality, P-chiral center and so on, have been developed. These ligands are applied to catalytic asymmetric reactions such as asymmetric hydrogenations, asymmetric allylations, asymmetric conjugate additions, asymmetric cycloadditions and asymmetric cross-coupling reactions by the combination with various transition metal species.

(S)-BINAP [B1405]

(R,R)-DIOP

(R,R)-DIPAMP

(R)-(S)-PPFA

[B3035]

[D2535]

etc.

[B1113]

B2711

B2710 P

Phosphine Ligands

B3450

Fe P

B1406 PPh2 PPh2

B2709

C(CH3)3 C(CH3)3 C(CH3)3

Fe P

CH(CH3)2

PPh2

PPh2

PPh2

PPh2

CH(CH3)2 CH(CH3)2

PPh2

CH(CH3)2

B1246

PPh2

B2704

CH3

P (CH2)4

P 2

P

P

CH3

2

B2027

B1959

B1113

CH3 PPh2 P CH2CH2 P

O PPh2

P

C(CH3)3

B1405

B1137 CH3

B3449

PPh2

Fe PPh2

P

(CH2)6 P

CH3 O CH3 O

H

H

CH2 P CH2 P

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

63

Cross-coupling Reaction Using Transition Metal Catalysts

Synthetic Organic Chemistry

B1112

B1982

CH3 O

CH2

P

CH3 O

CH2

P

B1960

P CH2

P

B2867

P

B1138

(C6H5)2P

(CH2)5 P

P CH2CH2CH2

O

B3035

B3036

C2979

OCH3

OCH3

PCH2CH2P

PCH2CH2P

CH3O

CH3O

C2980

D3940

Me P Me Me Me Me Me

D3387

C(CH3)3

D2411

(CH3)3C

P

P

C2981

Me

Materials Chemistry

P(C6H5)2

Me

Me

P

P

D3388

D3389 P

C(CH3)3

2

P

P

P C(CH3)3

(CH3)2N

D2535

D2536

D2775

CH3 N(CH3)2 PPh2

(CH3)2N Ph2P

Fe

T0361

T2584

E0519

Bu Bu

P

T0519

P CH2CH3

P

T1165

(CH3)3C P H

P Bu

tBu

CH2

P

T1643 O

C(CH3)3

Bu

t

Bu

OCH3 P(C6H5)2

Fe

T1912

t

D2766

CH3

BF4

P

O

C(CH3)3

T1614

P O

T0861

T1024

T1025

OCH3

CH3

OCH3 CH3

CH3

P

P

P

P

OCH3

CH3

P

3

CH3O

OCH3

CH3

CH3

T0862 CH3

P CH3

64

CH3

Product No.

Product Name

B2711 B2710 B3449 B3450 B1406 B1405

1,1'-Bis(di-tert-butylphosphino)ferrocene 1,1'-Bis(diisopropylphosphino)ferrocene (2R,3R)-(-)-2,3-Bis(diphenylphosphino)bicyclo[2.2.1]hept-5-ene ((2R,3R)-(-)-Norphos) (2S,3S)-(+)-2,3-Bis(diphenylphosphino)bicyclo[2.2.1]hept-5-ene ((2S,3S)-(+)-Norphos) (R)-(+)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl ((R)-(+)-BINAP) (S)-(-)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl ((S)-(-)-BINAP)

Unit Size 100mg 100mg

1g 1g 100mg 100mg 1g 5g 1g 5g

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Cross-coupling Reaction Using Transition Metal Catalysts

1,4-Bis(diphenylphosphino)butane 5g 100mg (2S,3S)-(-)-Bis(diphenylphosphino)butane ((S,S)-Chiraphos) 4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene (Xantphos) 1g 1,2-Bis(diphenylphosphino)ethane 10g 1,1'-Bis(diphenylphosphino)ferrocene 1g 5g 1,6-Bis(diphenylphosphino)hexane 1g (2R,3R)-(-)-1,4-Bis(diphenylphosphino)-2,3-O-isopropylidene-2,3-butanediol ((-)-DIOP) (2S,3S)-(+)-1,4-Bis(diphenylphosphino)-2,3-O-isopropylidene-2,3-butanediol ((+)-DIOP) Bis(diphenylphosphino)methane 5g 1,5-Bis(diphenylphosphino)pentane Bis[2-(diphenylphosphino)phenyl] Ether 5g 1,3-Bis(diphenylphosphino)propane 5g (R,R)-1,2-Bis[(2-methoxyphenyl)phenylphosphino]ethane ((R,R)-DIPAMP) (S,S)-1,2-Bis[(2-methoxyphenyl)phenylphosphino]ethane ((S,S)-DIPAMP) 100mg cBRIDP® 200mg Cy-cBRIDP® 200mg 200mg Cy-vBRIDP® Di-tert-butylphenylphosphine 2-(Di-tert-butylphosphino)biphenyl Dicyclohexylphenylphosphine 1g 2-(Dicyclohexylphosphino)biphenyl 1g 2-(Dicyclohexylphosphino)-2'-(dimethylamino)biphenyl 1g (R)-N,N-Dimethyl-1-[(S)-2-(diphenylphosphino)ferrocenyl]ethylamine ((R)-(S)-PPFA) (S)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine ((S)-(R)-PPFA) (S)-(-)-2-Diphenylphosphino-2'-methoxy-1,1'-binaphthyl 100mg 4-Diphenylphosphinomethyl Polystyrene Resin cross-linked with 2% DVB (200-400mesh) (0.5-1.0mmol/g) Ethyldiphenylphosphine Tri-tert-butylphosphine Tributylphosphine 25mL 100mL Tri-tert-butylphosphonium Tetrafluoroborate 1g Tricyclohexylphosphine (contains Tricyclohexylphosphine Oxide) (ca. 18% in Toluene, ca. 0.60mol/L) Tri(2-furyl)phosphine 1g Triphenylphosphine 25g Tris(2,6-dimethoxyphenyl)phosphine Tris(4-methoxyphenyl)phosphine 5g 5g Tri(o-tolyl)phosphine Tri(m-tolyl)phosphine 5g Tri(p-tolyl)phosphine 5g

Unit Size 25g 1g 5g 25g 25g 5g 1g 1g 25g 1g 25g 25g 100mg 1g 1g 1g 1g 5g 1g 5g 5g 5g 100mg 100mg 1g 5g 5g 5g 500mL 5g 25mL 5g 500g 25g 25g 25g 25g 25g

Materials Chemistry

Product Name

B1246 B2704 B2709 B1137 B2027 B1959 B1113 B1112 B1982 B1960 B2867 B1138 B3035 B3036 C2979 C2980 C2981 D3940 D3387 D2411 D3388 D3389 D2535 D2536 D2775 D2766 E0519 T1912 T0361 T2584 T1165 T1643 T0519 T1614 T0861 T1024 T1025 T0862

Synthetic Organic Chemistry

Product No.

References 1) J. F. Hartwig, in 2) Reviews for alkylbiaryl phosphine ligands: a) R. Martin, S. L. Buchwald, . 2008, , 1461. b) D. S. Surry, S. L. Buchwald, . 2008, , 6338. 3) Review for BRIDPs®: K. Suzuki, Y. Hori, Y. Nakayama, T. Kobayashi,

, Univ Science Books, 2009.

. 2011,

, 1231.

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

65

Cross-coupling Reaction Using Transition Metal Catalysts

Synthetic Organic Chemistry

-Heterocyclic Carbene (NHC) Ligands -Heterocyclic carbene (NHC) is a cyclic carbene species with two neighboring nitrogen atoms. NHC was discovered by Wanzlick . in 1968, and in 1991, it was isolated and structure determined by Arduengo . So, for their achievements, NHC is also called as the Wanzlick-Arduengo type carbene. Generally, NHC is hard to isolate as a single carbene monomer because it easily dimerizes or reacts with water to decompose. However, NHC is conformationally stabilized by introducing bulky substituents on the nitrogen atoms of NHC. NHC substituted by a mesityl groups or 2,6-diisopropylphenyl groups is commonly used as a ligand for organometallic complexes.

R

N

N

base

R

R

N

N

R

H N-Heterocyclic Carbene (NHC)

Materials Chemistry

R: Bulky substituent

N

N

N

IPr

N

N

IMes

N

N

SIPr

N

SIMes

A characteristic property of NHC ligands is their high coordinating ability caused by their bulkiness and strong electron-donating property. Their effect is stronger relative to trialkylphosphines, and allows the formation of metal-NHC complexes by ligand exchange reactions of metal-phosphine complexes with NHC ligands. In this way, NHC ligands strongly form complexes with some metals, and also produce coordinative unsaturation species by pushing out a position ligand coordinated with the metal center. Therefore, metal complexes coordinated by NHC ligands are highly active species but chemically stable and easy to handle, so they are expected to have a high turnover frequency. Metal-NHC complexes can be prepared by a complex-forming reaction of metal complexes having anionic ligands such as acetoxy ions with NHC which was previously prepared from imidazolium salts and bases. They can be also prepared the carbene-exchange reaction of silver-carbene complexes prepared from silver(I) oxide and imidazolium salts. This method is effective to use when bases are unavailable for preparing NHC. Metal-NHC complexes have been used for various chemical transformations such as cross-coupling reactions, cycloaddition reactions and C-H bond activation reactions since they have been successfully applied in metathesis reactions. In addition, NHC is used as an organocatalyst for benzoin condensations and acyloin condensations the umpolung process.

B3506

-Heterocyclic Carbene Ligands

B3465

B3158

N CH3 CH CH3

N

N CH3

CH3 CH CH3

CH3 CH3 CH3 CH CH3 CH

N

(CH3)2CH

N CH(CH3)2 CH(CH3)2

CH(CH3)2

N Cl

(CH3)2CH

CH(CH3)2

D3882

CH3 N

CH3

C CH3

N

CH3

N Cl

N

(CH3)2CH

D3472

CH3

CH3

CH3

66

N

N

N CH3 CH CH3 CH3 CH CH3

D3611

(CH3)2CH

D3711 CH3

CH3 CH CH3

B3157 CH3 CH CH3

BF4

(CH3)3C

N

N

C(CH3)3

CH3 C CH3 CH3

Availability or specification of the listed products are subject to change without prior notice.

N

Cl

Cl

Cross-coupling Reaction Using Transition Metal Catalysts

D3446

D3870 CH3

N

CH3

CH3

CH3

N CH3

Synthetic Organic Chemistry

CH3

N

N

Cl

CH3

CH3

CH3 CH3

CH3

CH3

Product Name

B3506 B3157 D3611 B3465 B3158 D3711 D3472 D3882 D3446 D3870

1,3-Bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene 1,3-Bis(2,6-diisopropylphenyl)imidazolinium Chloride (SIPr・HCl) 500mg 1,3-Bis(2,6-diisopropylphenyl)imidazolium Chloride (IPr・HCl) 500mg 1,3-Bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) 1,3-Bis(2,4,6-trimethylphenyl)imidazolinium Chloride (SIMes・HCl) 1,3-Di-tert-butylimidazolium Tetrafluoroborate (It Bu・HBF4) 1,3-Di-tert-butylimidazol-2-ylidene (It Bu) 1,3-Dicyclohexylimidazolium Chloride (IcHex・HCl) (This product is only available in Japan.) 1,3-Dimesitylimidazolium Chloride (IMes・HCl) 1,3-Dimesitylimidazol-2-ylidene (IMes)

Unit Size 1g 5g 25g 5g 5g 5g 5g 5g 5g 5g

1g 5g 1g 1g 1g 1g 1g 1g 1g

Materials Chemistry

Product No.

References , Wiley-VCH, Weinheim, 2006. , Univ Science Books, 2009.

1) S. P. Nolan, in 2) J. F. Hartwig, in

B0468

B2695 D0905

B1018 CH3 CH3 N

Bases & Additives

N N

B0709

C2430

CH3

CH3

N H

OCs

CsO

CsF

OCs

CH3

M0508

L0204 L0222

CH3

N CH3

N

CH3

LiCl

S0560

S0485

O

. HCl . H2O

KO

. H2O

CH3

P1758

N

N N

N

CH3

P1748

N

P0221

CH3

CH3

P0081

N

C(CH3)3 C(CH3)3

O

D1599

CH3

D3134

N

D0925 CH3

N

C2204

O

NH2

N CH3

N

C2160

CH3 CH3

CH3

O OK

KF

NaO

ONa

CH3ONa

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

67

Cross-coupling Reaction Using Transition Metal Catalysts

Synthetic Organic Chemistry

T0054

T0057

(CH2)3CH3 CH3(CH2)3 N

(CH2)3CH3

(CH2)3CH3 Br

CH3(CH2)3 N

Materials Chemistry

(CH2)3CH3

(CH2)3CH3

(CH2)3CH3

68

Z0015

I

Zn

Product No.

Product Name

B2695 D0905 B0468 B1018 B0709 C2430 C2160 C2204 D3134 D0925 D1599 L0204 L0222 M0508 P0221 P0081 P1748 P1758 S0560 S0485 T0054 T0057 Z0015

Bathophenanthroline (purified by sublimation) Bathophenanthroline 2,2'-Bipyridyl 1,8-Bis(dimethylamino)naphthalene [for Dehydrohalogenation] tert-Butylamine Cesium Acetate Cesium Carbonate Cesium Fluoride 4,4'-Di-tert-butyl-2,2'-bipyridyl Diisopropylamine N,N-Diisopropylethylamine Lithium Chloride Anhydrous Lithium Chloride (2.3% in Tetrahydrofuran, ca. 0.5mol/L) 1-Methylimidazole 1,10-Phenanthroline Monohydrate 1,10-Phenanthroline Hydrochloride Monohydrate Potassium Carbonate Potassium Fluoride Sodium Carbonate Sodium Methoxide Tetrabutylammonium Bromide Tetrabutylammonium Iodide Zinc (Powder)

Unit Size

Availability or specification of the listed products are subject to change without prior notice.

25g 1g 25mL

25mL 25mL

25g

25g 25g

1g 1g 5g 100g 500g 5g 25g 100mL 500mL 25g 100g 25g 100g 25g 100g 1g 5g 100mL 500mL 100mL 500mL 25g 300g 100mL 100g 500g 1g 25g 25g 300g 300g 300g 100g 500g 100g 500g 100g 500g 300g

Activation of Non-active Bonds

Synthetic Organic Chemistry

Activation of Non-active Bonds Recently, development of the methodology for activation of unreactive bonds with transition metals and applications for functional transformations have been actively performed. In this study, C-H bond activation is studied as low environmental load type of reactions because this type of reaction proceeds with the cross-coupling reactions without using halides or nucleophilic organometallic species, thereby decreasing the number of reaction steps. A reasonable expression for these functional transformations is “C-H bond transformation”or“C-H bond functionalization” . R

X + H

R'

or

R

H + M

R'

catalyst

R

catalyst

R'

H

+ H

R' Materials Chemistry

X H + or M

R

H + H

cf. Cross-coupling reactions R X

catalyst

+ R' M X

+

R

R'

M

In 1993, Murai . reported that the -position of a C-H bond of aromatic ketones was activated by the action of catalytic amounts of carbonyl(dihydrido)tris(triphenylphosphine)ruthenium(II) and consequently added to olefins siteselectively. After this report, the study of C-H bond activation reactions dramatically progressed.

O H

+

Si(OEt)3

RuH2(CO)(PPh3)3 (2 mol%) [C2251] toluene, reflux, 2 h

O Si(OEt)3

Functional transformation the activation of unreactive bonds is classified into two types of synthetic modes. One is a method to activate by the assist of intramolecular chelation from the directing group in which the activation of unreactive bonds is performed by oxidative addition of lower-valent metal species. The other method is to cleave relatively high acidic C-H bonds with higher-valent metal species. In this method, it is often necessary to use reoxidants for reproducing higher-valent metal species. Even in reactions using higher-valent metal species, the assist of intramolecular chelation from the directing group is effective for performing the activation of unreactive bonds regioselectively. Metal species utilized for functional transformation the activation of unreactive bonds are palladium, ruthenium, rhodium, iridium and so on, with most of them being noble metals. Recently, relatively inexpensive metals such as nickel, copper and iron have also been used in these transformations. Much research has been performed and a number of useful transformations such as arylations, alkenylations, alkynylations, carbonylations and heteroatom functionalizations have been reported. Many of them activate C-H bonds on unsaturated carbons of aromatic rings or alkenes to transform into other functional groups. However, currently, cleavage of C-H bonds on sp3 carbon which are generally harder to activate are being studied and successful transformations have been developed. There are various ways to activate unreactive bonds. The detail of these chemical properties and reactivities are explained as follows.

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

69

Activation of Non-active Bonds

Synthetic Organic Chemistry

B1676

B1374

B2018 CH3

Palladium

(CH3CN)2PdCl2

O

O CH CH C CH CH

2

Pd

Pd

O CH3

B3292

B2055

D4333

A1424 CH3

O

O S Pd

P

O C CH3

3

O C CH3

S O

P

O

Cl Cl

Cl

Materials Chemistry

O

PPh2

3

P1870

CH3

O

Pd

2

PPh2

Pd2

CH3 C O

2

O CF3

C O

2

Pd2

Pd Cl

Product No.

Product Name

B1676 B1374 B2018 B3292 B2055 D4333 A1424 P1870

Bis(acetonitrile)palladium(II) Dichloride Bis(dibenzylideneacetone)palladium(0) Bis(2,4-pentanedionato)palladium(II) 1,2-Bis(phenylsulfinyl)ethane Palladium(II) Diacetate Bis(tricyclohexylphosphine)palladium(II) Dichloride Dichloro[9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene]palladium(II) Palladium(II) Acetate Palladium(II) Trifluoroacetate

Unit Size

B1902

1g 1g 1g 200mg 1g 200mg 1g 1g

C2251

5g 5g 5g 1g 5g 1g 5g 5g

D2751 (CH3)2CH

Cl

Ruthenium

Cl

H

Ru Cl

P

Ru Cl

Ru

CH3 Cl

CO

Cl Ru

H

Ru Cl Cl CH(CH3)2

CH3 3

H1010

R0074

Cl Cl

Ru

Cl

Ru Cl

T2181

RuCl3

D1997

Ru(CO)4 (CO)4Ru

Ru(CO)4

P

Ru

Cl Cl

3

70

Product No.

Product Name

B1902 C2251 D2751 H1010 R0074 T2181 D1997

Benzeneruthenium(II) Chloride Dimer Carbonyl(dihydrido)tris(triphenylphosphine)ruthenium(II) Dichloro(p-cymene)ruthenium(II) Dimer (Hexamethylbenzene)ruthenium(II) Dichloride Dimer Ruthenium(III) Chloride Triruthenium Dodecacarbonyl Tris(triphenylphosphine)ruthenium(II) Dichloride

Unit Size

Availability or specification of the listed products are subject to change without prior notice.

1g 250mg 1g 1g 100mg 1g

5g 1g 5g 1g 5g 1g 5g

Activation of Non-active Bonds

B3961

B2091

BF4

BF4

Rh

Rh

2

Cl

Synthetic Organic Chemistry

Rhodium

C2253

Rh

Cl

Rh

C2461

B1045

N0453

P1788

R0069 CH3

CH3

CH2

CH2

CH2 Cl

Rh CH2

CH3

Cl

CH2

Rh

Cl

CH2

CH2

Cl

Rh

CH2

Rh

Rh

Cl

CH3

CH3

Rh Cl

CH3

O

CH3

Cl Rh Cl

O

Cl Rh Cl CH3

CH3

CH3

CH3

O O CH3(CH2)6

O

O O Rh

Rh O O

O

(CH2)6CH3

R

O

Rh O

H

H

R

. 2 CH3

O

R

O

H

OO

Rh Rh

O O O R

H R

O

O

O Cl

. 2 CH3

O

O

Cl Cl

O O O

R H

C OCH2CH3

O

O N

R=

O H

R

C OCH2CH3

R

O

. 2 CH3

R

O

C OCH2CH3

OO

R

O

R

O

R=

. 2 CH3

O Cl

N

O H

Cl

O

O

Cl Cl

C OCH2CH3

O O O H

Rh

Rh O

R

H R'

R

O

O

. CH3

R

H

H OO

O

R R=

O

. 2 CH3

O F

O

O

O

F F

C OCH2CH3

O O O

R H

CH2

O

C OCH2CH3

R

Ph Ph O

R H OO

Rh Rh

N

O H

F

R'=

N

R=

T1544

R

Rh Rh

R

OO

O O O H

R'

H R'

O

T2661 H

H

Rh Rh

N

R=

O H

Cl

Rh

R

T2660

R H

OO

Rh O O O

N

R=

H

O

O

T2659

O

H

OO

Rh O O O

R

O

H

H

R

R' H

R

H

T2658 H

T1551

R

(CH2)6CH3

R

T2055

O

Materials Chemistry

T2054 (CH2)6CH3

CH3 O O Rh

CH3

CH3

R0161

O

Rh O O

O

R R=

O

. 2 CH3

F

N

O H

F

O

O

F F

C OCH2CH3

Rh O O O Ph Ph Ph

Ph

Ph Ph Ph O O Ph Rh

O

O Ph Ph

. CH2Cl2

T0931

P 3

Rh

Cl

3

Product No.

Product Name

B3961 B2091 C2253 C2461 B1045 N0453 P1788 R0069 R0161 T2054 T2055 T1551 T2658 T2659 T2660 T2661 T1544 T0931

Bis(1,5-cyclooctadiene)rhodium(I) Tetrafluoroborate Bis[η-(2,5-norbornadiene)]rhodium(I) Tetrafluoroborate Chlorobis(cyclooctene)rhodium(I) Dimer Chlorobis(ethylene)rhodium(I) Dimer Chloro(1,5-cyclooctadiene)rhodium(I) Dimer Norbornadiene Rhodium(I) Chloride Dimer (Pentamethylcyclopentadienyl)rhodium(III) Dichloride Dimer Rhodium(II) Acetate Dimer Rhodium(II) Octanoate Dimer Tetrakis[N-phthaloyl-(R)-tert-leucinato]dirhodium Bis(ethyl Acetate) Adduct Tetrakis[N-phthaloyl-(S)-tert-leucinato]dirhodium Bis(ethyl Acetate) Adduct Tetrakis[N-phthaloyl-(S)-phenylalaninato]dirhodium Ethyl Acetate Adduct Tetrakis[N-tetrachlorophthaloyl-(R)-tert-leucinato]dirhodium Bis(ethyl Acetate) Adduct Tetrakis[N-tetrachlorophthaloyl-(S)-tert-leucinato]dirhodium Bis(ethyl Acetate) Adduct Tetrakis[N-tetrafluorophthaloyl-(R)-tert-leucinato]dirhodium Bis(ethyl Acetate) Adduct Tetrakis[N-tetrafluorophthaloyl-(S)-tert-leucinato]dirhodium Bis(ethyl Acetate) Adduct Tetrakis(triphenylacetato)dirhodium(II) Dichloromethane Adduct Tris(triphenylphosphine)rhodium(I) Chloride

Unit Size 100mg 1g 100mg 1g 100mg 500mg 200mg 100mg 1g 100mg 200mg 1g 100mg 1g 200mg 1g 100mg 100mg 100mg 50mg 100mg 50mg 100mg 100mg 1g 5g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

71

Activation of Non-active Bonds

Synthetic Organic Chemistry

C2252

C3040

Iridium

P

Ir

C2985

CO

P

Cl

Ir

2

C1807

C2662

Ir

Ir

Ir

Cl

O

I0616

Ir

Materials Chemistry

IrCl3

N

O

. xH2O

Ir O

PF6

CH3

Product No.

Product Name

C2252 C3040 C2985 C1807 C2662 C2824 I0616 T2557

Carbonylchlorobis(triphenylphosphine)iridium(I) Carbonylhydridotris(triphenylphosphine)iridium(I) Chlorobis(cyclooctene)iridium(I) Dimer Chloro(1,5-cyclooctadiene)iridium(I) Dimer (1,5-Cyclooctadiene)(methoxy)iridium(I) Dimer (1,5-Cyclooctadiene)(pyridine)(tricyclohexylphosphine)iridium(I) Hexafluorophosphate Iridium(III) Chloride Hydrate Tris(2,4-pentanedionato)iridium(III)

3

Unit Size

B2225

B2226 Ph

Nickel

Ni

P Ph

B3534

Cl

Ph

P

O 3

Ni O

P 2

Ph P Ph NiCl2 P Ph

B0034

Cl

Ph3P

Cl

Ph3P

Ni

Ni

1g 1g 200mg 250mg 1g 200mg 1g 100mg 1g 5g 1g

Ph

Cl Cl

Ph P

Cl Ni Cl

P Ph

Ph

B1571

CH3

Fe

Cl

200mg 200mg

B1313

Ph P

CH3

Ir

CH3 3

CH3

N0096

Cl

T2557

P Ir

O

Cl

Ir

H

3

C2824 CH3

Cl

CO

Ph

N0850

O Ni

S O O

2

. 6H2O

NiCl2

2

3

T0276

N0861 O

CH3

Ni2

SO3

. 6H2O

CF3

2

72

Ni2

S O O

2

Product No.

Product Name

B2225 B2226 B1313 N0096 B3534 B1571

[1,2-Bis(diphenylphosphino)ethane]nickel(II) Dichloride [1,1'-Bis(diphenylphosphino)ferrocene]nickel(II) Dichloride [1,3-Bis(diphenylphosphino)propane]nickel(II) Dichloride Bis(2,4-pentanedionato)nickel(II) Hydrate Bis(tricyclohexylphosphine)nickel(II) Dichloride Bis(triphenylphosphine)nickel(II) Dichloride

Unit Size

Availability or specification of the listed products are subject to change without prior notice.

1g

5g 1g 5g 25g 1g 10g

25g 5g 25g 500g 5g 100g

Activation of Non-active Bonds

Product Name

B0034 N0850 T0276 N0861

Nickel(II) Benzenesulfonate Hexahydrate Nickel(II) Chloride Anhydrous Nickel(II) p-Toluenesulfonate Hexahydrate Nickel(II) Trifluoromethanesulfonate

Unit Size Synthetic Organic Chemistry

Product No.

25g 500g 25g 5g

25g 1g

T2994

Gold

P

Product Name

T2994

(Triphenylphosphine)gold(I) Chloride

Cl

Materials Chemistry

Product No.

Au

Unit Size 200mg

C0384

C2304

1g

C2346 (CH3)2CH

CH3 N

O

Copper

Cu O CH3

N (CH3)2CH

CH(CH3)2 Cu Cl CH(CH3)2

O

Cu2

CH3 C O

2

. H2O

2

T1292 O CF3

Cu2

S O O

2

Product No.

Product Name

C0384 C2304 C2346 T1292

Bis(2,4-pentanedionato)copper(II) Chloro[1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene]copper(I) Copper(II) Acetate Monohydrate Copper(II) Trifluoromethanesulfonate

Unit Size 25g 200mg 25g 5g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

250g 1g 500g 25g

73

Activation of Non-active Bonds

Synthetic Organic Chemistry

Mechanism of C-H Bond Cleavage and Regioselectivity Mechanism of a C-H bond cleavage for aromatic rings is classified into four types of modes according to the metal complexes and reactants. (I) Oxidative addition by low-valent metal species (II) Electrophilic aromatic substitution (SEAr) by high-valent metal species (III) Concerted metalation-deprotonation (CMD) by high-valent metal species (IV) σ-Bond metathesis

Materials Chemistry

In (I), oxidative addition by low-valent metal species needs the assist of intramolecular chelation from the directing group. In (II) and (III), the C-H bond cleavage by high-valent metal species, it is mostly necessary to add reoxidants for reproducing higher-valent metal species. (I) Oxidative addition Hydrides remain on the metals. Low-valent metals Ru(0), Rh(I), Pd(0), Ni(0) etc. are used. Effective to assist intramolecular chelation from the directing group



(I)

H

H Mn

Mn+2

(II) Electrophilic aromatic substitution (SEAr) Hydrogen atom is pulled out as a proton. Reactive to electron-rich aromatic rings and five-membered heterocycles Generally, not rate-limiting step and low KIE(kH/kD=1.2~2.0)

‡ (II) M H

M X H O

(III) R

-HX ‡

(III) Concerted metalation-deprotonation (CMD) Hydrogen atom is pulled out as a proton. Reactive to fluorine or nitrogen substituted electron-poor aromatic rings If C-H bond cleavage is rate-limiting step, showed high KIE(kH/kD=3.5~7.0)

M O

H

M

- RCO2H ‡

(IV)

M R H

(IV) σ-Bond metathesis Hydrogen atom is pulled out as a hydrocarbon. Early transition metal complexes with unsaturated coordination state Activation of sp3 C-H bonds

-RH

In C-H bond activations, it is important that there is an assist of intramolecular chelation from the directing group (DG), because the generated carbon-metal-hydrogen bonding (C-M-H) species by oxidative addition of low-valent metal species are thermally unstable chemical species. However, the thermal stability of C-M-H species is increased by intramolecular coordination from heteroatoms on the directing group, and thereby, the formed metallacycles allow the C-H bond to cleave. Also, by the direction of intramolecular chelation from the directing group, the vicinal position of C-H bonds to the directing group in aromatic rings and the vicinal position of C-H bonds to the hetero atom in heterocycles are regioselectively activated. This synthetic manner can be applied for C-H bond activations by high-valent metal species. M

DG

DG

H

M H DG:Directing Group

R DG:

Z

R O

N

R'

N

R

NMe2

R

OMe

O

Z= O, NR, S

R= Me, H, OR, NR2

H N

R= Me, NMe2

CN

etc...

Recently, auxiliary groups aimed at C-H bond activations have been developed. They are effectively used for difficult-to-perform C-H bond activations by simple auxiliary groups. F O

F

CF3

N H

F F

N

O N H

Si N

i-Pr

i-Pr

Auxiliary groups aimed at C-H bond activations

When using substrates with highly acidic hydrogen atoms caused by orientation and heteroaromatics with relatively highly acidic hydrogen atoms, the acidic hydrogen atoms can be cleaved by high-valent metal species. In this reaction, the regioselective C-H bond activations are performed without the assist from the directing groups. 74

Availability or specification of the listed products are subject to change without prior notice.

Activation of Non-active Bonds

Synthetic Organic Chemistry

Typical Reaction Modes by C-H Bond Cleavage Arylations and alkenylations I. Ar-H/Ar-X Coupling (Pd, Ni, Cu, Fe etc.) (X= I, Br etc.)

Ar

II. Ar-H/Ar-M Coupling (Ru, Rh, Pd, Ni etc.) (M= B etc.)

Ar

H + X

R

or

H + M

catalyst

R

or

III. Ar-H/Ar-H Coupling (Pd(II), Rh(III) etc.) cross-dehydrogenative coupling (CDC)

Ar

H + H

Ar

R

R= aryl, alkenyl

R

Materials Chemistry

Addition of alkenes and alkynes Oxidative addition Electrophilic aromatic substitution (SEAr) by low-valent metal species by high-valent metal species

R

cat. M

+

R

or

R'

H

R R

R +

Y

R

DG

R R

DG

Y'

cat. M

Y'

or

Y'

H

Y

Y

Low-valent metal catalyst: RuH2(CO)(PPh3)3, Ru3(CO)12, RhCl(PPh3)3 etc. High-valent metal catalyst: Pd(OAc)2, (Cp*RhCl2)2 etc.

Carbonylations

CO insertion R

DG OH

R

R

DG CO

+

cat. M

H

O DG

O

conditions Pd(II) cat., acid, oxidant, CO (1 atm) or Ru(0), Rh(I) cat. CO (high pressure), alkene

R

R

DG R O

Heteroatom functionalizations R

H Y +

Y

H

H

R

Y

R +

cat. M

or

E

Y cat. M

R E

M= Ir, Rh, Ru, Pt etc. Y= SiR3, B(OR)2

M= Pd(II) etc. E: OR, OCOR NRR', NCOR SR, SO2R I, Br, Cl, F

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

75

Metal Reagents for Organic Synthesis

Synthetic Organic Chemistry

Metal Reagents for Organic Synthesis

A0963

A1554

B1883 B3976 CH2MgBr

CH2

Grignard Reagents

Materials Chemistry

B1933

B1884

B0726

C1504 MgBr

CH3 C MgCl

MgBr

CH3

MgCl

CH3

C2039 MgBr

MgCl

CH3

CH3 CH3

C1505

MgBr

B1148 B1147

CH2MgCl

CH2

D3551

E0778 E0135

E0497 E0134 MgBr

MgBr

CH3

CH3

MgBr

CH3

MgCl

CH3

F0673

H0822

H0821

I0517

I0518

MgBr CH3

CH3

MgBr

CH3

MgBr

CH3

MgBr CH3

CH3

MgBr

F

I0654

I0543 I0542

CH3

CH3 CH3

MgCl

P1251

CH3

M0364

M0362 M0785

MgCl

. LiCl

P1177

CH3MgBr

P2025

CH3MgI

P1381

CH3(CH2)14MgBr

P0880

T1698

MgBr

T1699

P0191

T1700 MgBr

MgBr

MgI

T1451 T2609 CH3

CH3

CH3 CH3

76

MgBr

MgBr

MgBr CH3

CH3

MgCl

MgBr CH3

O0240

Si CH3

CH3

Availability or specification of the listed products are subject to change without prior notice.

CH2MgCl

Metal Reagents for Organic Synthesis

V0053

Synthetic Organic Chemistry

CH2 CHMgBr

Product Name

A0963 A1554 B1883 B3976 B1933 B1884 B1148 B1147 B0726 C1504 C1505 C2039 D3551 E0497 E0134 E0778 E0135 F0673 H0822 H0821 I0517 I0518 I0543 I0542 I0654 M0362 M0785 M0364 O0240 P1251 P1177 P2025 P1381 P0191 P0880 T1698 T1699 T1700 T1451 T2609 V0053

Allylmagnesium Bromide (ca. 13% in Ethyl Ether, ca. 0.7mol/L) Allylmagnesium Chloride (ca. 11% in Tetrahydrofuran, ca. 1.0mol/L) Benzylmagnesium Bromide (ca. 12% in Tetrahydrofuran, ca. 0.6mol/L) Benzylmagnesium Bromide (ca. 18% in Tetrahydrofuran, ca. 0.9mol/L) Benzylmagnesium Chloride (ca. 16% in Tetrahydrofuran, ca. 1mol/L) sec-Butylmagnesium Bromide (ca. 16% in Tetrahydrofuran, ca. 1mol/L) tert-Butylmagnesium Chloride (23% in Tetrahydrofuran, ca. 2mol/L) tert-Butylmagnesium Chloride (26% in Ethyl Ether, ca. 2mol/L) Butylmagnesium Chloride (23% in Tetrahydrofuran, ca. 2mol/L) Cyclohexylmagnesium Bromide (ca. 18% in Tetrahydrofuran, ca. 1mol/L) Cyclopentylmagnesium Bromide (ca. 18% in Tetrahydrofuran, ca. 1mol/L) Cyclopropylmagnesium Bromide (ca. 10% in Tetrahydrofuran, ca. 0.7mol/L) (2,5-Dimethylphenyl)magnesium Bromide (20% in Tetrahydrofuran, ca. 1mol/L) Ethylmagnesium Bromide (13% in Tetrahydrofuran, ca. 1mol/L) Ethylmagnesium Bromide (39% in Ethyl Ether, ca. 3mol/L) Ethylmagnesium Chloride (ca. 1.0mol/L in Tetrahydrofuran) activated with Zinc Chloride (ca. 10mol%) Ethylmagnesium Chloride (ca. 18% in Tetrahydrofuran, ca. 2mol/L) 4-Fluorophenylmagnesium Bromide (ca. 19% in Tetrahydrofuran, ca. 1.0mol/L) Heptylmagnesium Bromide (21% in Tetrahydrofuran, ca. 1mol/L) Hexylmagnesium Bromide (20% in Tetrahydrofuran, ca. 1mol/L) Isobutylmagnesium Bromide (17% in Tetrahydrofuran, ca. 1mol/L) Isopropylmagnesium Bromide (15% in Tetrahydrofuran, ca. 1mol/L) Isopropylmagnesium Chloride (ca. 11% in Tetrahydrofuran, ca. 1mol/L) Isopropylmagnesium Chloride (ca. 13% in Ethyl Ether, ca. 1mol/L) Isopropylmagnesium Chloride - Lithium Chloride (15% in Tetrahydrofuran, ca. 1mol/L) Methylmagnesium Bromide (12% in Tetrahydrofuran, ca. 1mol/L) Methylmagnesium Bromide (35% in Ethyl Ether, ca. 3mol/L) Methylmagnesium Iodide (33% in Ethyl Ether, ca. 2mol/L) n-Octylmagnesium Bromide (ca. 22% in Tetrahydrofuran, ca. 1mol/L) Pentadecylmagnesium Bromide (ca. 15% in Tetrahydrofuran, ca. 0.4mol/L) Pentylmagnesium Bromide (18% in Tetrahydrofuran, ca. 1mol/L) Phenylmagnesium Bromide (16% in Tetrahydrofuran, ca. 1mol/L) Phenylmagnesium Chloride (27% in Tetrahydrofuran, ca. 2mol/L) Phenylmagnesium Iodide (ca. 42% in Ethyl Ether, ca. 2mol/L) Propylmagnesium Bromide (ca. 27% in Tetrahydrofuran, ca. 2mol/L) o-Tolylmagnesium Bromide (ca. 17% in Tetrahydrofuran, ca. 0.9mol/L) m-Tolylmagnesium Bromide (19% in Tetrahydrofuran, ca. 1mol/L) p-Tolylmagnesium Bromide (19% in Tetrahydrofuran, ca. 1mol/L) Trimethylsilylmethylmagnesium Chloride (20% in Ethyl Ether, ca. 1mol/L) Trimethylsilylmethylmagnesium Chloride (ca. 18% in Tetrahydrofuran, ca. 1mol/L) Vinylmagnesium Bromide (14% in Tetrahydrofuran, ca. 1mol/L)

Unit Size

A1222

B1974 (CH2)3CH3

Alkyl Metal Reagents

CH3(CH2)3

Sn CH2CH (CH2)3CH3

CH3(CH2)3

B1975

(CH2)3CH3

CH2 CH3(CH2)3 Sn C C Sn (CH2)3CH3 CH3(CH2)3

100mL 100g Price on request 100g 250g 100g 250g 250g 250g 100g 100g 100g 100g 250g 250g 250g 250g 250g 250g 250g 250g 250g 250g 250g 100mL 250g 250g 100g 250g 250g 250g 250g 250g 250g 250g 100g 100g 100g 100mL 100mL 100g

Materials Chemistry

Product No.

(CH2)3CH3

(CH2)3CH3 CH3(CH2)3

Sn

CH3(CH2)3 Sn

(CH2)3CH3

(CH2)3CH3

CH3(CH2)3

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

77

Metal Reagents for Organic Synthesis

Synthetic Organic Chemistry

B1832

B4209

B0396

Sn

CH3

(CH2)3CH3

Al

Li

CH3

D1338

D1373

CH3 Sn CH3 Cl

H0842

M1655

M0589

P1429

T1750

C CH

CH3

T1866

Si CH2 CH3

(CH2)3CH3

(CH2)3CH3 Sn

(CH2)3CH3

CH3(CH2)3 Sn

(CH2)3CH3

CH CH2

(CH2)3CH3

(CH2)3CH3 CH3(CH2)3 Sn H (CH2)3CH3

(CH2)3CH3

T0784

Al

CH3

CH3

CH3

(CH2)3CH3

Si C C Sn CH3

(CH2)3CH3

(CH2)3CH3

CH3

CH3 Al

CH3

CH3 CH3

T0782 T1575

CH3

CH3

Sn CH3 CH3

T1865

(CH2)3CH3

T0783 T0925

CH3 CH3

(CH2)3CH3

T1473

CH3(CH2)3 Sn F

OH

T0919

CH3(CH2)3 Sn (CH2)3CH3

CH2CH CH2

(CH2)3CH3

T1794

CH3

Cl

Sn

(CH2)3CH3

CH2CH CH2 CH2 CHCH2 Sn CH2CH CH2

(CH2)3CH3 Cl

CH3

T0058

T0678

CH3(CH2)3 Sn

(CH2)3CH3

CH3

CH3

T0363 (CH2)3CH3

CH3CH2 Al

O

Li Cl

CH3

M0744

CH3HgI

T2009

Al

Sn

Cl

O CH3(CH2)7 Sn (CH2)7CH3

CH3HgCl

C1411

Ti

O CH3

E0648

M0258

CH3Li

Li

(CH2)3CH3

Cl

Zn(CH2CH3)2

Cl

CH3(CH2)3 Sn

Sn

Cl

CH3

CH3

CH3(CH2)3

CH3

D3902 D3214

CH3

Materials Chemistry

Cl Li

C

CH3(CH2)3 (CH2)3CH3

D1340

D0305

CH3

CH3(CH2)3 (CH2)3CH3 CH3(CH2)3 Sn

D0223

CH3

CH3

Al

CH3

CH3

T0958 CH3 CH3

Sn Cl CH3

78

Product No.

Product Name

A1222 B1974 B1975 B1832 B4209 B0396

Allyltributyltin Bis(tributylstannyl)acetylene trans-1,2-Bis(tributylstannyl)ethylene Bis(tributyltin) tert-Butyllithium (ca. 18% in Pentane, ca. 1.9mol/L) Butyllithium (ca. 15% in Hexane, ca. 1.6mol/L)

Unit Size

Availability or specification of the listed products are subject to change without prior notice.

5g 1g 1g 5g

25g 5g 5g 25g 100mL 100mL 500mL

Metal Reagents for Organic Synthesis

Dibutyltin Dichloride Dibutyltin Oxide Diethylaluminum Chloride (ca. 15% in Hexane, ca. 0.87mol/L) Diethylzinc (ca. 15% in Toluene, ca. 1mol/L) Diethylzinc (ca. 17% in Hexane, ca. 1mol/L) Dimethyltin Dichloride Di-n-octyltin Oxide Ethylaluminum Dichloride (17% in Hexane, ca. 1mol/L) Hexyllithium (30% in Hexane, ca. 2.3mol/L) Methyllithium (ca. 3-5% in Ethyl Ether, ca. 1-2mol/L) Methylmercuric Chloride Methylmercuric Iodide Monobutyltin Oxide Phenyllithium (ca. 16% in Butyl Ether, ca. 1.6mol/L) Tebbe Reagent (ca. 0.5mol/L in Toluene) Tetraallyltin Tetrabutyltin Tetramethyltin Tributylethynyltin Tributyltin Chloride Tributyltin Fluoride Tributyltin Hydride (stabilized with BHT) [Reducing Reagent] Tributyl(trimethylsilylethynyl)tin Tributyl(trimethylsilylmethyl)tin Tributylvinyltin Triethylaluminum (15% in Hexane, ca. 1.0mol/L) Triethylaluminum (15% in Toluene, ca. 1.1mol/L) Triisobutylaluminum (15% in Hexane, ca. 0.50mol/L) Trimethylaluminum (15% in Hexane, ca. 1.4mol/L) Trimethylaluminum (15% in Toluene, ca. 1.8mol/L) Trimethyltin Chloride

Unit Size 25g 100g

25g

25g

100mL 100g 25g

25g

1g 25g 5g 1g 100g

25g

25g 5g 1g

5g

5g

A0775

A1601 O

Metallocenes

B0886

B2711

B4272

O P

C Fe

Fe

P

B2027

B3374

Fe PPh2

B3501

Fe

O

B O

O

CH3 CH3 CH3 CH3

Ph P Ph NiCl2 P Ph

B2227

Fe

PPh2

Fe

CH(CH3)2

Ph P Ph PdCl2 P Ph

R

. CH2Cl2

Fe

R

N

Fe

R=

CH

CH3 CH3

O

Ph

B2063

B0885 CH3

(CH2)3CH3

C CH3

NH C OC(CH3)3 Fe

CH(CH3)2 CH(CH3)2

B3197

O

Br Fe

Fe

Ph

CH3 CH3

O

P

Ph2P

CH(CH3)2

B2064

Fe

Ph

B3476

B

Fe PCl2

Ph P Ph CoCl2 P Ph

Fe

P

Fe

B2226

PPh2

B3196

PCl2

C(CH3)3

Fe

Fe

B2710

C(CH3)3 C(CH3)3 C(CH3)3

NH2

C CH3

Ferrocenes

500g 500g 100mL 100mL 500mL 500g 500g 100mL 100mL 100mL 5g 25g 500g 100mL 25mL 5g 500g 25g 5g 500g 25g 250g 25g 5g 25g 100mL 100mL 100mL 100mL 100mL 25g

Materials Chemistry

Product Name

D0223 D0305 D1340 D3902 D3214 D1338 D1373 E0648 H0842 M1655 M0589 M0258 M0744 P1429 C1411 T2009 T0058 T0919 T1750 T0363 T0678 T1473 T1865 T1866 T1794 T0783 T0925 T0784 T0782 T1575 T0958

Synthetic Organic Chemistry

Product No.

Fe

CH3

Fe

CH3 CH3

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

79

Metal Reagents for Organic Synthesis

Synthetic Organic Chemistry

F0312

F0313

B0913

B0915

D2829

O

O

C CH3 Fe

D1272

D2951

C CH3

C

O

O

D1271

D2537 CH2N

C CH2CH2CH3 Fe

D2538

CH3

Fe

Materials Chemistry

D2536

D1273

CH3

D2529

Fe

Fe

CH

D0444

F0406

F0280 O

CH3 CH2CH3

CH3

CH2

Fe

Fe PPh2 O

F0165

N(CH3)2

Fe

CH3

E0394 N

CH3

N(CH3)2

Fe

Fe

D3822

CH3

CH3

(CH3)2N Ph2P

Fe

Ph2P

D2528

CH3

N(CH3)2 PPh2

(CH3)2N Ph2P

PPh2

O

D2535

CH3

N(CH3)2 PPh2

CH3

C CH2CH2CH3

(CH2)3CH3

Br

CH3

Fe

Fe

Fe

Fe

O (CH2)3CH3

Br

C

Fe

Fe

Fe

F0664

F0320 O

Fe

Fe

F0286 O

C OH

B(OH)2

C OH

Fe

Fe

B0914

O

C

Fe

O

CH3

CH2CH2 C OH

CH2 N

(CH2)11CH3

CH3

Fe

Fe

B(OH)2

B(OH)2

C OH

Br

C OH O

F0166

F0167

H0941

CH3 CH2

Br

I0749

80

O

CH

S

C O N Fe

T2546 O

O

CH3

Fe

Fe

Fe

T2545 O

CH3

CH2OH

CHCH3

Fe

I

S0820 N

Fe

CH3

OH

C NHNH2

CH2 N CH3 Fe

H0464

O

CH3

N CH3 CH3

Fe

H0463

V0064 O

CH3

S

CH

CH3

Fe

CH2

Fe

O

Product No.

Product Name

A0775 A1601 B0886 B2711 B4272 B2710

Acetylferrocene Aminoferrocene Benzoylferrocene 1,1'-Bis(di-tert-butylphosphino)ferrocene 1,1'-Bis(dichlorophosphino)ferrocene 1,1'-Bis(diisopropylphosphino)ferrocene

Unit Size

Availability or specification of the listed products are subject to change without prior notice.

10g 100mg 5g 100mg 200mg 100mg

25g 1g 25g 1g 1g 1g

Metal Reagents for Organic Synthesis

(R,R '')-2,2''-Bis(diphenylphosphino)-1,1''-biferrocene 1,1'-Bis(diphenylphosphino)ferrocene 1g [1,1'-Bis(diphenylphosphino)ferrocene]cobalt(II) Dichloride [1,1'-Bis(diphenylphosphino)ferrocene]nickel(II) Dichloride 1g [1,1'-Bis(diphenylphosphino)ferrocene]palladium(II) Dichloride Dichloromethane Adduct (S,S '')-2,2''-Bis[(S)-4-isopropyloxazolin-2-yl]-1,1''-biferrocene 1,1'-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)ferrocene Bromoferrocene N-(tert-Butoxycarbonyl)aminoferrocene tert-Butylferrocene Butylferrocene Cyclohexenylferrocene Cyclopentenylferrocene 1,1'-Diacetylferrocene 1,1'-Dibenzoylferrocene 1,1'-Dibromoferrocene 1,1'-Dibutylferrocene 1,1'-Dibutyrylferrocene N,N-Dimethylaminomethylferrocene (R)-N,N-Dimethyl-1-[(S)-1',2-bis(diphenylphosphino)ferrocenyl]ethylamine (S)-N,N-Dimethyl-1-[(R)-1',2-bis(diphenylphosphino)ferrocenyl]ethylamine (R)-N,N-Dimethyl-1-[(S)-2-(diphenylphosphino)ferrocenyl]ethylamine (S)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine 1,1'-Dimethylferrocene (R)-(+)-N,N-Dimethyl-1-ferrocenylethylamine (S)-(-)-N,N-Dimethyl-1-ferrocenylethylamine (S)-1-(Diphenylphosphino)-2-[(S)-4-isopropyloxazolin-2-yl]ferrocene Ethylferrocene Ferrocene 25g Ferroceneacetic Acid Ferroceneboronic Acid (contains varying amounts of Anhydride) [Cyclic boronating reagent for GC/MS] Ferrocenecarboxylic Acid 1g 1,1'-Ferrocenediboronic Acid (contains varying amounts of Anhydride) 1,1'-Ferrocenedicarboxylic Acid 3-Ferrocenoylpropionic Acid (Ferrocenylmethyl)dodecyldimethylammonium Bromide (Ferrocenylmethyl)trimethylammonium Bromide (Ferrocenylmethyl)trimethylammonium Iodide (Hydrazinocarbonyl)ferrocene [for HPLC Labeling] 1-Hydroxyethylferrocene Hydroxymethylferrocene (S)-(4-Isopropyloxazolin-2-yl)ferrocene N-Succinimidyl Ferrocenecarboxylate (R)-(p-Toluenesulfinyl)ferrocene (S)-(p-Toluenesulfinyl)ferrocene Vinylferrocene

Unit Size

B1951

C1589

D3307

100mg 500mg 5g 25g 1g 5g 1g 5g 5g 25g 100mg 500mg 1g 5g 1g 5g 1g 1g 5g 10g 25g 25g 25g 5g 5g 25g 1g 5g 1g 5g 5g 25g 5g 25g 100mg 100mg 100mg 100mg 5g 25g 200mg 1g 200mg 1g 200mg 1g 5g 100g 500g 1g 5g 100mg 1g 5g 25g 1g 1g 5g 25g 5g 1g 5g 5g 1g 1g 5g 1g 5g 1g 200mg 1g 1g 5g 1g 1g

Materials Chemistry

Product Name

B3196 B2027 B3374 B2226 B2064 B3197 B3501 B3476 B2227 B2063 B0885 F0312 F0313 B0913 B0915 D2829 D1272 D2951 D1271 D2537 D2538 D2535 D2536 D1273 D2528 D2529 D3822 E0394 D0444 F0406 F0280 F0165 F0664 B0914 F0320 F0286 F0166 F0167 H0941 H0463 H0464 I0749 S0820 T2545 T2546 V0064

Synthetic Organic Chemistry

Product No.

D3321 CH3

CH3 CH3

Others

Fe

Co

PF6

PF6

CH3 CH3

Cl

Zr Cl

CH3 CH3

CH3 CH3

(CH2)3CH3 Cl

Zr

Cl (CH2)3CH3

CH3

D4100

D3286

H0914

I0645

CH2CH2CH3 CH3 Ti

CH3

Cl

Hf

Cl

Cl CH2CH2CH3

Hf

Cl

CH3 CH3

D1574

C

Zr

Cl Cl

Ni

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

81

Metal Reagents for Organic Synthesis

Synthetic Organic Chemistry

R0078

C1411

Ru

Ti

Z0009

CF3SO3

T1658

Cl

Al

CH3 CH3

Z0010

Zr SO3CF3

.

T0616

O

V0090

O

F3C S O Ti

Cl

O S CF3

O

Ti

Cl

Cl

V Cl

O

Z0007

H

Zr

Cl

Cl

Zr

Cl

Materials Chemistry

O

Product No.

Product Name

B1951 C1589 D3307 D3321 D4100 D3286 H0914 I0645 D1574 R0078 C1411 T1658 T0616 V0090 Z0009 Z0010 Z0007

η-Benzene(η-cyclopentadienyl)iron(II) Hexafluorophosphate Bis(cyclopentadienyl)cobalt(III) Hexafluorophosphate Decamethylzirconocene Dichloride 1,1'-Dibutylzirconocene Dichloride Dimethyltitanocene (5% in Tetrahydrofuran/Toluene) 1,1'-Dipropylhafnocene Dichloride Hafnocene Dichloride 1,1'-Isopropylidenezirconocene Dichloride Nickelocene Ruthenocene Tebbe Reagent (ca. 0.5mol/L in Toluene) Titanocene Bis(trifluoromethanesulfonate) Titanocene Dichloride Vanadinocene Dichloride Zirconocene Bis(trifluoromethanesulfonate) Tetrahydrofuran Adduct Zirconocene Chloride Hydride Zirconocene Dichloride

Unit Size

C2201

Half Metallocenes

C1994

Ph3P Ru PPh3 Cl

1g

1g

1g

1g

100mg 5g

Ti

Cl

Cl

1g 5g 5g

1g

C1995

Cl

5g

5g 1g 1g 5g 100g 1g 25g 100mg 5g 1g 25mL 1g 25g 1g 5g 25g 25g

I0646

Cl

Zr

Cl

Cl

Cl

Ti

Cl

Cl

P1651 CH3 CH3

CH3

CH3 Cl

82

Ti Cl

CH3 Cl

Product No.

Product Name

C2201 C1994 C1995 I0646 P1651

Cyclopentadienylbis(triphenylphosphine)ruthenium(II) Chloride Cyclopentadienyltitanium(IV) Trichloride Cyclopentadienylzirconium(IV) Trichloride (Indenyl)titanium(IV) Trichloride (Pentamethylcyclopentadienyl)titanium(IV) Trichloride

Unit Size

Availability or specification of the listed products are subject to change without prior notice.

1g 1g 1g

5g 5g 5g 1g 1g

Metal Reagents for Organic Synthesis

Synthetic Organic Chemistry

Typical Metal Reagents Li (Lithium) Product Name

B4209 B0396 B4697 P1049 D4395 H0842 L0060 L0191 A1478 L0203 L0170 L0267 B2542 H0915 L0186 L0210 L0253 L0224 L0204 L0222 L0171 F0171 L0146 H1057 L0225 H0580 L0144 P0659 S0237 L0133 L0158 L0159 L0164 L0190 T1548 L0240 M1655 L0080 P1429

tert-Butyllithium (ca. 18% in Pentane, ca. 1.9mol/L) Butyllithium (ca. 15% in Hexane, ca. 1.6mol/L) Butyllithium (ca. 20% in Cyclohexane, ca. 2.3mol/L) Dilithium Phthalocyanine Dilithium Tetrachlorocopper(II) (ca. 2.5% in Tetrahydrofuran, ca. 0.1mol/L) Hexyllithium (30% in Hexane, ca. 2.3mol/L) Lithioncarmine (powder) Lithium Acetate Lithium Acetoacetate Lithium Aluminum Hydride (Powder) Lithium Aluminum Hydride (10% in Tetrahydrofuran, ca. 2.5mol/L) Lithium Bis(pentafluoroethanesulfonyl)imide Lithium Bis(trifluoromethanesulfonyl)imide Lithium Bis(trimethylsilyl)amide (ca. 26% in Tetrahydrofuran, ca. 1.3mol/L) Lithium Borohydride (ca. 3mol/L in Tetrahydrofuran) Lithium Bromide Lithium tert-Butoxide (ca. 10% in Tetrahydrofuran, ca. 1mol/L) Lithium Carbonate Lithium Chloride Anhydrous Lithium Chloride (2.3% in Tetrahydrofuran, ca. 0.5mol/L) Lithium Diisopropylamide (ca. 20% in Tetrahydrofuran/Ethylbenzene/Heptane, ca. 1.5mol/L) Lithium Formate Monohydrate Lithium Hexafluorophosphate Lithium 1,1,2,2,3,3-Hexafluoropropane-1,3-disulfonimide Lithium Hydroxide Anhydrous Lithium DL-2-Hydroxybutyrate Lithium L-Lactate Lithium Pyruvate Monohydrate [Guaranteed for Standard to GOT, GPT] Lithium Stearate Lithium Tetrafluoroborate Lithium Tetrakis(pentafluorophenyl)borate - Ethyl Ether Complex Lithium Tri-tert-butoxyaluminum Hydride (ca. 30% in Tetrahydrofuran, ca. 1.0mol/L) Lithium Tri-sec-butylborohydride (ca. 21% in Tetrahydrofuran, ca. 1.0mol/L) Lithium Triethylborohydride (ca. 12% in Tetrahydrofuran, ca. 1.0mol/L) Lithium Trifluoromethanesulfonate Lithium Trifluoro(trifluoromethyl)borate - Dimethyl Carbonate Complex Methyllithium (ca. 3-5% in Ethyl Ether, ca. 1-2mol/L) (2,4-Pentanedionato)lithium Phenyllithium (ca. 16% in Butyl Ether, ca. 1.6mol/L)

Unit Size 100mL 100mL 500mL 100mL 500mL 1g 100mL 500mL 100mL 1g 25g 500g 1g 5g 25g 100g 100mL 1g 25g 250g 100mL 500mL 100mL 25g 100g 500g 100mL 25g 500g 25g 300g 100mL 100mL 500mL 25g 500g 25g 100g 1g 5g 25g 100g 500g 5g 25g 25g 25g 25g 500g 25g 1g 5g 100mL 100mL 100mL 500mL 25g 1g 5g 100mL 25g 500g 100mL

Materials Chemistry

Product No.

Na (Sodium)(excluding simple sodium salts) Product No.

Product Name

C0075 C0076 C1374 D1331 D0923 D1930 P0973 M0632 M0096 S0489 H0894 S0480 S0396 D1003 D2479 D0716 S0548 S0547 E0195 S0392 S0481 M0057

Chloramine B Hydrate 25g 500g Chloramine T Trihydrate 25g 500g o-Chloramine T 25g 5,5-Diphenylhydantoin Sodium Salt 25g 500g 1g Dipicrylamine Sodium Salt (contains 10% Water) Disodium Dimercaptomaleonitrile 1g 5g Disodium Phthalocyanine 1g 5g 2-Mercaptopyridine N-Oxide Sodium Salt (40% in Water, ca. 3.3mol/L) 25g 500g Methyl Mercaptan Sodium Salt (ca. 15% in Water) 25g 500g Sodium Azide 100g 100mL 500mL Sodium Bis(trimethylsilyl)amide (contains 2-Methyl-2-butene) (38% in Tetrahydrofuran, ca. 1.9mol/L) Sodium Borohydride 25g 100g 500g Sodium Cyanoborohydride [Reducing Agent] 5g 25g 250g Sodium Dichloroisocyanurate 25g 500g Sodium Diformylamide 25g 25g 500g Sodium Dimethyldithiocarbamate Dihydrate Sodium Ethoxide (ca. 20% in Ethanol) 500mL Sodium Ethoxide 100g Sodium Ethylxanthate 25g 500g Sodium Hexafluorophosphate 25g 100g 500g Sodium Hydride (60%, dispersion in Paraffin Liquid) Sodium 2-Mercaptobenzothiazole 25g 500g

Unit Size

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

83

Synthetic Organic Chemistry

Metal Reagents for Organic Synthesis

Product No.

Product Name

S0486 S0485 S0540 A5131

Sodium Methoxide (ca. 5mol/L in Methanol) Sodium Methoxide Sodium Tetrachloropalladate(II) Sodium Tetrakis(4-fluorophenyl)borate Hydrate [Precipitation reagent for Cs and titrimetric reagent for

Unit Size

A5130 T0193 S0394 B0131

Sodium Tetraphenylborate [Precipitation reagent for K] Sodium 2-Thiobarbiturate Sodium Triacetoxyborohydride o-Sulfobenzimide Sodium Salt Dihydrate

nonionic surfactants]

100mL 500mL 100g 500g 1g 1g 1g 25g 25g 25g

5g 10g 500g 100g 500g

Materials Chemistry

K (Potassium)(excluding simple potassium salts)

84

Product No.

Product Name

A1490 B1124 B4377 C0714 I0223 I0019 I0220 N0428 P0097 P0179 P0403 P1480 H0893 P1681 P1807 P1008 P2155 B0747 P1613 E0194 G0160 H0817 H1058 H0652 P0309 I0023 P1808 I0177 P2153 T1083 N0006 O0056 O0164 P0534 R0058 S0057 S0164 P2168 A5132 P1380 P2114 P1692 P0475 P1479 P0988 P0989 S0156 S0903 A5107

Acesulfame K Bismuthiol II Hydrate Bismuth Tripotassium Dicitrate Carbazole Potassium Salt Indigodisulfonic Acid Dipotassium Salt Indigotetrasulfonic Acid Tetrapotassium Salt Hydrate Indigotrisulfonic Acid Potassium Salt 4-Nitrocatechol Sulfate Dipotassium Salt Hydrate [Substrate for Sulfatase] Phenolphthalein Disulfate Potassium Salt Hydrate N-Phenylglycine Potassium Salt Phthalimide Potassium Salt Potassium Allyltrifluoroborate Potassium Bis(trimethylsilyl)amide (11% in Toluene, ca. 0.5mol/L) Potassium Borohydride Potassium (Bromomethyl)trifluoroborate Potassium tert-Butoxide Potassium [[(tert-Butoxycarbonyl)amino]methyl]trifluoroborate Potassium Butylxanthate Potassium Cyanide Potassium Ethylxanthate Potassium Guaiacolsulfonate Hemihydrate Potassium Hexafluoroarsenate Potassium 1,1,2,2,3,3-Hexafluoropropane-1,3-disulfonimide Potassium Hyaluronate from Cockscomb Potassium Hydrogen Phthalate Potassium 3-Indoleacetate Potassium (Iodomethyl)trifluoroborate Potassium Isopropylxanthate Potassium (Methoxymethyl)trifluoroborate Potassium Monomethyl Terephthalate Potassium 1-Naphthaleneacetate Potassium Oleate Potassium Oxonate Potassium Propylxanthate Potassium Rhodizonate Potassium Sorbate Potassium Sulfamate Potassium Tetracyanoborate Potassium Tetrakis(4-chlorophenyl)borate [Anion for the neutral carrier type ion electrode] Potassium Tri-sec-butylborohydride (ca. 1.0mol/L in Tetrahydrofuran) Potassium Trifluoroacetate Potassium Trifluoro(trifluoromethyl)borate Potassium Trihydrogen Dioxalate Dihydrate [for Determination of pH] Potassium Vinyltrifluoroborate Pyridoxylidene-L-glutamic Acid Dipotassium Salt Pyridoxylidene-L-isoleucine Potassium Salt Sinigrin Hydrate Sinigrin TBPE (=Tetrabromophenolphthalein Ethyl Ester Potassium Salt)

Unit Size

T0036 F0027

Tetrabromofluorescein Potassium Salt Uranine K

[Sensitive spectrophotometric reagent for amines, quaternary ammonium salts and other cations]

Availability or specification of the listed products are subject to change without prior notice.

25g

100g 5g 1g

500g 25g 5g 25g 1g 1g 1g 5g 1g 1g 5g 25g 500g 25g 500g 1g 5g 100mL 500mL 25g 100g 1g 5g 25g 100g 500g 1g 5g 25g 25g 25g 100g 500g 25g 10g 1g 5g 1g 25g 500g 1g 25g 1g 5g 25g 1g 25g 500g 25g 25g 500g 5g 25g 25g 1g 25g 500g 100g 200mg 1g 5g Price on request 25g 1g 5g 25g 25g 500g 1g 5g 1g 1g 100mg 100mg 1g 25g 25g

Metal Reagents for Organic Synthesis

Product No.

Product Name

F0172

Formic Acid Rubidium Salt

Synthetic Organic Chemistry

Rb (Rubidium) Unit Size 5g

Cs (Cesium) Product No.

Product Name

C2430 C2202 C2160 C2203 C2204 C2205

Cesium Acetate Cesium Bromide Cesium Carbonate Cesium Chloride Cesium Fluoride Cesium Iodide

Unit Size 25g 25g 25g 25g

100g 25g 100g 100g 100g 25g

Be (Beryllium) Product Name

B0454 B4720

Bis(2,4-pentanedionato)beryllium(II) Bis[2-(2-pyridinyl)phenolato]beryllium(II)

Unit Size 5g 200mg

Materials Chemistry

Product No.

Mg (Magnesium) Product No.

Product Name

A0963 A1554 A0484 A5353 B1883 B3976 B1933 H0556 M0001 T0749 B1884 B1148 B1147 B0726 B4643 C0780 C1504 C1505 D4683 D3551 E0094 E0497 E0134 E0778 E0135 F0673 H0822 H0821 I0517 I0518 I0543 I0542 I0654 E0396 G0276 M0938 P0108 P1018 M2209 S0238 T1304 M0362 M0785 M0364 M0927 O0240

Allylmagnesium Bromide (ca. 13% in Ethyl Ether, ca. 0.7mol/L) Allylmagnesium Chloride (ca. 11% in Tetrahydrofuran, ca. 1.0mol/L) 8-Anilino-1-naphthalenesulfonic Acid Magnesium(II) Salt Hydrate ANS-Mg (=Magnesium 8-Anilino-1-naphthalenesulfonate) [Hydrophobic fluorescent probe] Benzylmagnesium Bromide (ca. 12% in Tetrahydrofuran, ca. 0.6mol/L) Benzylmagnesium Bromide (ca. 18% in Tetrahydrofuran, ca. 0.9mol/L) Benzylmagnesium Chloride (ca. 16% in Tetrahydrofuran, ca. 1mol/L) Bis(hexafluoroacetylacetonato)magnesium(II) Hydrate Bis(2,4-pentanedionato)magnesium(II) Bis(trifluoro-2,4-pentanedionato)magnesium(II) Hydrate sec-Butylmagnesium Bromide (ca. 16% in Tetrahydrofuran, ca. 1mol/L) tert-Butylmagnesium Chloride (23% in Tetrahydrofuran, ca. 2mol/L) tert-Butylmagnesium Chloride (26% in Ethyl Ether, ca. 2mol/L) Butylmagnesium Chloride (23% in Tetrahydrofuran, ca. 2mol/L) sec-Butylmagnesium Chloride - Lithium Chloride (15% in Tetrahydrofuran, ca. 1.2mol/L) Chlorophyll (Total Chlorophyll: ca. 6.0%) Cyclohexylmagnesium Bromide (ca. 18% in Tetrahydrofuran, ca. 1mol/L) Cyclopentylmagnesium Bromide (ca. 18% in Tetrahydrofuran, ca. 1mol/L) Di-sec-butylmagnesium - Lithium Chloride (13% in Tetrahydrofuran, ca. 0.8mol/L) (2,5-Dimethylphenyl)magnesium Bromide (20% in Tetrahydrofuran, ca. 1mol/L) Ethylenediaminetetraacetic Acid Magnesium Disodium Salt Hydrate Ethylmagnesium Bromide (13% in Tetrahydrofuran, ca. 1mol/L) Ethylmagnesium Bromide (39% in Ethyl Ether, ca. 3mol/L) Ethylmagnesium Chloride (ca. 1.0mol/L in Tetrahydrofuran) activated with Zinc Chloride (ca. 10mol%) Ethylmagnesium Chloride (ca. 18% in Tetrahydrofuran, ca. 2mol/L) 4-Fluorophenylmagnesium Bromide (ca. 19% in Tetrahydrofuran, ca. 1.0mol/L) Heptylmagnesium Bromide (21% in Tetrahydrofuran, ca. 1mol/L) Hexylmagnesium Bromide (20% in Tetrahydrofuran, ca. 1mol/L) Isobutylmagnesium Bromide (17% in Tetrahydrofuran, ca. 1mol/L) Isopropylmagnesium Bromide (15% in Tetrahydrofuran, ca. 1mol/L) Isopropylmagnesium Chloride (ca. 11% in Tetrahydrofuran, ca. 1mol/L) Isopropylmagnesium Chloride (ca. 13% in Ethyl Ether, ca. 1mol/L) Isopropylmagnesium Chloride - Lithium Chloride (15% in Tetrahydrofuran, ca. 1mol/L) Magnesium(II) 2-Ethylbutyrate Magnesium(II) Gluconate Hydrate Magnesium 4-Nitrobenzyl Malonate Hydrate Magnesium Phenoxyacetate Dihydrate Magnesium(II) Phthalocyanine Magnesium Porphyrin Magnesium(II) Stearate Magnesium Trifluoromethanesulfonate Methylmagnesium Bromide (12% in Tetrahydrofuran, ca. 1mol/L) Methylmagnesium Bromide (35% in Ethyl Ether, ca. 3mol/L) Methylmagnesium Iodide (33% in Ethyl Ether, ca. 2mol/L) Monoperoxyphthalic Acid Magnesium Salt Hexahydrate n-Octylmagnesium Bromide (ca. 22% in Tetrahydrofuran, ca. 1mol/L)

Unit Size 100mL 100g 25g 1g Price on request 100g 250g 1g 25g 5g 100g 250g 250g 250g 100mL 25g 100g 100g 100mL 100g 25g 250g 250g 250g 250g 250g 250g 250g 250g 250g 250g 250g 100mL 25g 25g 500g 25g 25g 1g 100mg 25g 250g 5g 25g 250g 250g 100g 25g 500g 250g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

85

Synthetic Organic Chemistry

Metal Reagents for Organic Synthesis

Product No.

Product Name

P1251 P1177 P2025 P1381 P0191 P0880 T1698 T1699 T1700 T2966 T1451 T2609 V0053

Pentadecylmagnesium Bromide (ca. 15% in Tetrahydrofuran, ca. 0.4mol/L) Pentylmagnesium Bromide (18% in Tetrahydrofuran, ca. 1mol/L) Phenylmagnesium Bromide (16% in Tetrahydrofuran, ca. 1mol/L) Phenylmagnesium Chloride (27% in Tetrahydrofuran, ca. 2mol/L) Phenylmagnesium Iodide (ca. 42% in Ethyl Ether, ca. 2mol/L) Propylmagnesium Bromide (ca. 27% in Tetrahydrofuran, ca. 2mol/L) o-Tolylmagnesium Bromide (ca. 17% in Tetrahydrofuran, ca. 0.9mol/L) m-Tolylmagnesium Bromide (19% in Tetrahydrofuran, ca. 1mol/L) p-Tolylmagnesium Bromide (19% in Tetrahydrofuran, ca. 1mol/L) Trimagnesium Dicitrate Nonahydrate Trimethylsilylmethylmagnesium Chloride (20% in Ethyl Ether, ca. 1mol/L) Trimethylsilylmethylmagnesium Chloride (ca. 18% in Tetrahydrofuran, ca. 1mol/L) Vinylmagnesium Bromide (14% in Tetrahydrofuran, ca. 1mol/L)

Unit Size 250g 250g 250g 250g 250g 250g 100g 100g 100g 25g 500g 100mL 100mL 100g

Materials Chemistry

Ca (Calcium) Product No.

Product Name

A0422 A2476 C0930 A0738 C2789 G0037 G0232 G0095 G0200 H0917 H0651 L0006 L0043 O0076 M0548 M0549 K0021 K0022 K0023 P0012 C2003 P0503 S0054 S0236 T0002 T0004 T0902 T1799 C0849 D1869 E0088 F0372 L0075 P0274 P0410

4-Aminosalicylic Acid Calcium Salt Heptahydrate Atorvastatin Calcium Salt Trihydrate Bis(2,4-pentanedionato)calcium(II) Calcium Alginate Calcium Dobesilate Hydrate Calcium Gluconate Monohydrate Calcium DL-Glycerate Hydrate Calcium Glycerophosphate Hydrate Calcium Glycolate Calcium 3-Hydroxy-3-methylbutyrate Hydrate Calcium 2-Hydroxy-4-(methylthio)butyrate Calcium Lactobionate Hydrate Calcium Levulinate Dihydrate Calcium Mesoxalate Trihydrate Calcium Methacrylate Hydrate Calcium Methanesulfonate Calcium 3-Methyl-2-oxobutyrate Hydrate Calcium 3-Methyl-2-oxovalerate Hydrate Calcium 4-Methyl-2-oxovalerate Hydrate Calcium D-Pantothenate Calcium Phthalate Hydrate Calcium Propionate Calcium Sorbate Calcium Stearate Calcium DL-Tartrate Tetrahydrate Calcium meso-Tartrate Trihydrate Calcium Thioglycolate Trihydrate Calcium L-Threonate 4-Chlorobenzoyl-L-tryptophan Calcium Salt Diethylenetriaminepentaacetic Acid Calcium Trisodium Salt Hydrate Ethylenediaminetetraacetic Acid Calcium Disodium Salt Hydrate Fenoprofen Calcium Salt Dihydrate Lithol Rubin BCA Phosphocholine Chloride Calcium Salt Tetrahydrate Phytin

Unit Size 25g 1g 25g 25g 25g

25g 5g 5g 25g 5g 25g 25g 1g 25g

25g

25g 25g

500g 5g 25g 500g 1g 500g 10g 500g 25g 25g 25g 25g 25g 5g 25g 500g 5g 25g 25g 500g 25g 500g 25g 500g 25g 25g 500g 25g 25g 25g 500g 25g 25g 250g 500g

Ba (Barium)

86

Product No.

Product Name

A0760 C0078 C0978 D0876 E0085 S0235 G0052 I0039 L0074 M0046 P0257 P0258 R0026

Barium Acrylate Monomer Barium Chloranilate Trihydrate Barium 2-Cyanoethylphosphate Hydrate [Phosphorylating Agent] Barium Diphenylamine-4-sulfonate Barium Disodium Ethylenediaminetetraacetate Hydrate Barium Stearate D-Glucose 6-Phosphate Barium Salt Heptahydrate Inosine 5'-Monophosphate Barium Salt Hydrate Lake Red CBA Mannose-6-phosphate Barium Salt Hydrate 6-Phosphogluconate Barium Salt Hydrate 3-Phospho-D-glyceric Acid Barium Salt Dihydrate Ribose-5-phosphate Barium Salt Hydrate

Unit Size

Availability or specification of the listed products are subject to change without prior notice.

25g 25g 5g 25g 1g 5g 25g 25g 25g 500g 100mg 1g 100mg 25g 100mg Price on request 1g 100mg 1g

Metal Reagents for Organic Synthesis

Product Name

A0244 A0804 A1831 A0245 A1200 A0246 B1895 D1340 D2972 D2971 E0648 L0203 L0170 L0159 M1211 M0468 M0469 C1167 P2280 P1944 S0467 C1411 T0783 T0925 T0784 T0782 T1575 A0241 T2238 T1527 A1267

Aluminum sec-Butoxide 25g 500g Aluminum tert-Butoxide 5g Aluminum(III) Chloride 100g 500g Aluminum Ethoxide 25g 250g Aluminum Glycinate 25g 500g Aluminum Isopropoxide 100g 500g Bis(2-ethylhexanoato)hydroxyaluminum 25g 250g 100mL Diethylaluminum Chloride (ca. 15% in Hexane, ca. 0.87mol/L) Diisobutylaluminum Hydride (17% in Toluene, ca. 1.0mol/L) 100mL 500mL 100mL 500mL Diisobutylaluminum Hydride (19% in Hexane, ca. 1.0mol/L) Ethylaluminum Dichloride (17% in Hexane, ca. 1mol/L) 100mL Lithium Aluminum Hydride (Powder) 25g 100g Lithium Aluminum Hydride (10% in Tetrahydrofuran, ca. 2.5mol/L) 100mL Lithium Tri-tert-butoxyaluminum Hydride (ca. 30% in Tetrahydrofuran, ca. 1.0mol/L) 100mL 50mL Methylaluminum Bis(2,6-di-tert-butyl-4-methylphenoxide) (0.4mol/L in Toluene) Mucicarmine 25g Mucicarmine Solution acc. to Mayer 500mL Phthalocyanine Chloroaluminum 1g 1g 5g Polydimethylsilane supported Palladium/Alumina Hybrid Catalyst [=Pd / (PMPSi-Al2O3)] Poly(methylphenyl)silane supported Palladium/Alumina Hybrid Catalyst [=Pd / (PSi-Al2O3)] 1g Sodium Bis(2-methoxyethoxy)aluminum Dihydride (70% in Toluene, ca. 3.6mol/L) 25g 100g 500g Tebbe Reagent (ca. 0.5mol/L in Toluene) 25mL Triethylaluminum (15% in Hexane, ca. 1.0mol/L) 100mL 100mL Triethylaluminum (15% in Toluene, ca. 1.1mol/L) Triisobutylaluminum (15% in Hexane, ca. 0.50mol/L) 100mL Trimethylaluminum (15% in Hexane, ca. 1.4mol/L) 100mL Trimethylaluminum (15% in Toluene, ca. 1.8mol/L) 100mL Tris(2,4-pentanedionato)aluminum(III) 25g 100g 500g 5g Tris(8-quinolinolato)aluminum (purified by sublimation) Tris(8-quinolinolato)aluminum 25g 250g Tris(trifluoro-2,4-pentanedionato)aluminum(III) 5g 25g

Unit Size

Materials Chemistry

Product No.

Synthetic Organic Chemistry

Al (Aluminum)

Ga (Gallium) Product No.

Product Name

G0359

Gallium(III) Chloride Anhydrous

Unit Size 5g

25g

In (Indium) Product No.

Product Name

I0778 I0020

Indium(III) Chloride Anhydrous Tris(2,4-pentanedionato)indium(III)

Unit Size 5g

25g 10g

Tl (Thallium) Product No.

Product Name

C0954 T1351

Cyclopentadienyl Thallium Thallium(III) Trifluoroacetate

Unit Size 5g 10g

Sn (Tin) Product No.

Product Name

A2170 A1222 A1491 B4685 B4437 B4378 T0650 B1974 B1975 B0907 B1832 B4536 B4453 D2466

Allenyltributyltin Allyltributyltin Allyltriphenyltin 4,8-Bis(2-butyl-n-octyloxy)-2,6-bis(trimethylstannyl)benzo[1,2-b:4,5-b ']dithiophene 4,8-Bis[5-(2-ethylhexyl)thiophen-2-yl]-2,6-bis(trimethylstannyl)benzo[1,2-b:4,5-b ']dithiophene 4,8-Bis(n-octyloxy)-2,6-bis(trimethylstannyl)benzo[1,2-b:4,5-b ']dithiophene Bis(2,4-pentanedionato)tin(IV) Dichloride Bis(tributylstannyl)acetylene trans-1,2-Bis(tributylstannyl)ethylene Bis(tributylstannyl) Sulfide Bis(tributyltin) 2,5-Bis(trimethylstannyl)thieno[3,2-b]thiophene 4,7-Bis(5-trimethylstannyl-2-thienyl)-2,1,3-benzothiadiazole Dibutyltin Bis(trifluoromethanesulfonate)

Unit Size 5g 5g

1g 1g 1g 5g 200mg

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

1g 25g 25g 200mg 200mg 200mg 25g 5g 5g 5g 25g 1g 200mg 5g

87

Materials Chemistry

Synthetic Organic Chemistry

Metal Reagents for Organic Synthesis

Product No.

Product Name

D0302 D0223 D0303 D0304 D0305 D1338 D4649 D1373 D2358 H1312 M1494 M0744 P1282 S0909 T2009 T1592 T0058 T0919 T0165 T2053 T3149 T2940 P1024 P0997 T1194 T3191 T1750 T1797 T2995 T3046 T1736 T1798 T0677 T0363 T0678 T1473 T1865 T1866 T1794 T1742 T1928 T0958 T0447

Dibutyltin Diacetate Dibutyltin Dichloride Dibutyltin Dilaurate Dibutyltin Maleate (so called) [for PVC stabilizer] Dibutyltin Oxide Dimethyltin Dichloride Dimethyltin Oxide Di-n-octyltin Oxide Diphenyltin Sulfide [Activator for O-Glycoside Synthesis] Hexamethylditin Methyl Tributylstannyl Sulfide Monobutyltin Oxide Phenyltin Trichloride SnAP-TM Reagent Tetraallyltin Tetrabutylammonium Difluorotriphenylstannate Tetrabutyltin Tetramethyltin Tetraphenyltin Tin(IV) Chloride (ca. 1.0mol/L in Dichloromethane) Tin(II) 2-Ethylhexanoate Tin(IV) 2,3-Naphthalocyanine Dichloride Tin(II) Phthalocyanine Tin(IV) Phthalocyanine Dichloride Tin(II) Trifluoromethanesulfonate Tributyl(1-ethoxyvinyl)tin Tributylethynyltin Tributyl(2-furyl)tin Tributyl(4-methoxy-2-pyridyl)tin Tributyl(1-phenyl-5-pyrazolyl)tin Tributyl(2-pyridyl)tin Tributyl(2-thienyl)tin Tributyltin Acetate Tributyltin Chloride Tributyltin Fluoride Tributyltin Hydride (stabilized with BHT) [Reducing Reagent] Tributyl(trimethylsilylethynyl)tin Tributyl(trimethylsilylmethyl)tin Tributylvinyltin Trimethyl(2-pyridyl)tin Trimethyl(4-pyridyl)tin Trimethyltin Chloride Triphenyltin Chloride

Unit Size 25g 25g 25g

100g 25g 100g 25g 100g 25g 25g 25g 1g 25g 25g 5g 200mg 1g 1g 25g 5g

100g 200mg 1g 1g

1g

25g

5g 1g 1g 1g 1g 5g 5g 100g 25g 5g

1g

5g 1g 1g 5g

500g 500g 500g 500g 500g 500g 100g 500g 1g 5g 100g 500g 25g 1g 5g 5g 500g 25g 25g 100mL 500g 1g 5g 1g 25g 5g 5g 5g 5g 5g 25g 25g 25g 500g 25g 250g 25g 5g 25g 5g 5g 25g 5g

Pb (Lead)

88

Product No.

Product Name

E0093 L0279 N0339 L0230 P0766 L0021 T0164

Ethylenediaminetetraacetic Acid Lead(II) Disodium Salt Hydrate Lead(II) Iodide [for Perovskite precursor] Lead Naphthenate Lead(II) Phthalocyanine (purified by sublimation) Lead(II) Phthalocyanine Lead Tetraacetate (contains Acetic Acid) Tetraphenyl Lead

Unit Size

Availability or specification of the listed products are subject to change without prior notice.

25g 1g 200mg 1g 25g

500g 5g 25g 1g 25g 500g 5g

Stable Lewis Acids in Aqueous Media

OTMS +

Ph

HCHO aq.

Yb(OTf)3 (20 mol%) [T1610] H2O – THF

Synthetic Organic Chemistry

Stable Lewis Acids in Aqueous Media 1)

O Ph

OH

Y. 1st run 2nd run 3rd run

94% 91% 93%

2) Yb(OTf)3 (20 mol%) [T1610]

CHO

CHO

CH2Cl2, 0 °C

Y. 1st run 2nd run

Materials Chemistry

+

77% (exo : endo = 93 : 7) 75% (exo : endo = 92 : 8)

The Lewis acid-catalyzed C-C bond forming reactions have been of great interest in organic synthesis. While various kinds of Lewis acid-promoted reactions have been developed, these reactions must be carried out under strict anhydrous conditions. The presence of even a small amount of water stops the reaction, because most Lewis acid immediately react with water rather than the substrates and decompose or deactivate. Recently, Kobayashi and co-worker have found that certain metal triflates are stable Lewis acids in aqueous media. The reaction of silyl enol ethers with commercial formaldehyde solution smoothly proceeds in aqueous media by the certain metal triflates, especially Yb(OTf)3 to give the corresponding aldol adducts in high yields. Moreover, the triflates can also be used in organic solvents in many reactions. In all cases, the reaction is completed by only a catalytic amount of the triflate, and the catalyst can be easily recovered after the reaction was completed and can be reused. On the other hand, in asymmetric synthesis, chiral Lewis acid which was prepared by Sc(OTf)3, chiral binaphthol and an amine affords chiral Diels-Alder adduct in the reactions of dienophiles and dienes. Then, the certain metal triflates, especially Yb(OTf)3, Sc(OTf)3, etc. are expected to be useful as new types of Lewis acid catalysts in many organic reactions. From the view points of green chemistry, these are also remarkably effective Lewis Acids as non-toxic and nonflammable water can be used as reaction solvent.

T1918

T1292 O

CF3

CF3

CF3

T1921

T1920

CF3

S OAg O

3

La3

S O O

4

CF3

3

T1610 O

O Sc3

S O

CF3

InCl3

O Tm3

S O O

3

CF3

Yb3

S O O

3

. xH2O

T1294 O

CF3

O

T1331

O

3

O Hf4

S O

O Nd3

S O O

CF3

2

T1663 O

T1293

O Cu2

S O O

3

T1919

CF3

I0778

O Ce3

S O O

T1708

O Y3

S O O

3

CF3

Zn2

S O O

2

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

89

Synthetic Organic Chemistry

Stable Lewis Acids in Aqueous Media

Product No.

Product Name

T1918 T1292 T1708 I0778 T1293 T1919 T1663 T1331 T1920 T1610 T1921 T1294

Cerium(III) Trifluoromethanesulfonate Copper(II) Trifluoromethanesulfonate Hafnium(IV) Trifluoromethanesulfonate Indium(III) Chloride Anhydrous Lanthanum(III) Trifluoromethanesulfonate Neodymium(III) Trifluoromethanesulfonate Scandium(III) Trifluoromethanesulfonate Silver Trifluoromethanesulfonate Thulium(III) Trifluoromethanesulfonate Ytterbium(III) Trifluoromethanesulfonate Hydrate Yttrium(III) Trifluoromethanesulfonate Zinc(II) Trifluoromethanesulfonate

Unit Size 5g 5g 1g 5g 5g 5g 1g 10g 5g 5g

25g 25g 5g 25g 25g 25g 5g 25g 5g 25g 25g 25g

References Materials Chemistry

1) Aldol reactions in aqueous media S. Kobayashi, . 1991, 2187; S. Kobayashi, I. Hachiya, . 1992, , 1625. 2) Reusable catalysts for Michael and Diels-Alder reactions S. Kobayashi, I. Hachiya, T. Takahori, M. Araki, H. Ishitani, . 1992, , 6815. 1994, 689; S. Kobayashi, I. Hachiya, 3) Reviews: S. Kobayashi, 1995, , 370; T. Ogino, T. Onozawa, 2000, number Ishikawa, , 2; S. Kobayashi, T. Hamada, S. Nagayama, K. Manabe, , 627; S. Kobayashi, . 2007, , 235.

90

Availability or specification of the listed products are subject to change without prior notice.

, 1998,

, 71; K. . 2001,

Ligands

Synthetic Organic Chemistry

Ligands Phosphine Ligands (see p.62) -Heterocyclic Carbene (NHC) Ligands (see p.66) A0005

B2283

B2281 O

CH2CH2

Ene Ligands F

C0513

C0468

C0503

C0505

C1689

D0443

H0084

H0087

I0016 I0354

CH3

CH3 CH2

CH2 CH3

CH3

CH3

CH3

CH3 CH3

CH3

M1425

M1411 CH3

Materials Chemistry

C0572

F

N0346

N0166

P1292 CH3

CH3

CH3

CH3

CH3 CH3

CH3

P1633

T1333

T0470 CH3

CH3

CH3

Product No.

Product Name

A0005 B2283 B2281 C0572 C0468 C0503 C0505 C1689 C0513 D0443 H0084 H0087 I0016 I0354

Acenaphthylene trans,trans-1,5-Bis(4-fluorophenyl)-1,4-pentadien-3-one 1,2-Bis(3-indenyl)ethane 1,3,5-Cycloheptatriene 1,4-Cyclohexadiene (stabilized with BHT) 1,5-Cyclooctadiene [stabilized with Octadecyl 3-(3',5'-Di-tert-butyl-4'-hydroxyphenyl)propionate] 1,3,5,7-Cyclooctatetraene (stabilized with HQ) 1H-Cyclopenta[l]phenanthrene p-Cymene Dicyclopentadiene (stabilized with BHT) [precursor to Cyclopentadiene] 1,5-Hexadiene Hexamethylbenzene Indene Indene

Unit Size 5g 1g 10mL 25mL 100mL 1mL 100mg 25mL 25mL 25mL 25mL 100mL

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

25g 25g 5g 25mL 25mL 500mL 5mL 1g 500mL 500mL 500mL 5g 500mL 25mL

91

Synthetic Organic Chemistry

Ligands

Product No.

Product Name

M1425 M1411 N0346 N0166 P1292 P1633 T1333 T0470

2-Methylbenzo[e]indene (mixture of 1H- and 3H-form) 2-Methylcyclopenta[l]phenanthrene 2,5-Norbornadiene (stabilized with BHT) 2-Norbornene 1,2,3,4,5-Pentamethylcyclopentadiene 1,2,3,4,5-Pentaphenyl-1,3-cyclopentadiene 1,2,3,4-Tetraphenyl-1,3-cyclopentadiene 1,3,5-Trimethylbenzene

Unit Size 100mg 1g 100mg 1g 25mL 100mL 500mL 25g 400g 5mL 25mL 100mg 1g 1g 5g 25mL 500mL

Materials Chemistry

P0052

A0881

A0869 O

O

Diketone Ligands

B1733

CH3

B1457

O

O

CH3O

O

C CH2

C

B3382

C1277

D0039

CH3

CH3 O

D1729 O

O CH3

E0405

CH3

C CH2 C

C CH3

O

Cl

CH3

D1678

O

CH3

O

CH3

C CH2 C

CH3

CH3

F0083

H1395

O

O

CH3

O

CH3

CH3

CH3

H0476

C CH2 C

N

O

CH3

O

O

O

O

C

CH2 C CF3

O

O

CH3

CH3

CH3

N

O

M1272

O

CH3

O

D2512

O O

O C CH3

C CH3

O

O

CH3

CH

C CH3

CH3

D0910

CH3

CH3

CH3O

O

CH3

D2413

CF3(CF2)2 C CH2 C C CH3

O

O O

OCH3

C CH3 O

O O

O

C CH3 CH3

O

C CH2 C CH3

O

CH3

CH3

CF3

CF3

CH3

M0597

M1132

P0160

P1297

T2037 O

CH3

O

O

O

CH3

CH3

T0434

92

CH3

O

CH3

CH3

O CH3

CH2

CH3

C

(CF2)6CF3

C

(CF2)6CF3

O

T0437 O

O

O

CH3 C CH2 C

CH3

T1583

O CF3

O

O

T0438 O

O CF3

F 3C

T2997 O

O O S

O

C CH2 C CF3

O

CF3 CH3

Availability or specification of the listed products are subject to change without prior notice.

Ligands

Acetylacetone 2-Acetylcyclohexanone 2-Acetylcyclopentanone 1,3-Bis(4-methoxyphenyl)-1,3-propanedione 3-Butyl-2,4-pentanedione 1-(4-tert-Butylphenyl)-3-(4-methoxyphenyl)-1,3-propanedione 3-Chloroacetylacetone Dehydroacetic Acid 2,2-Dimethyl-6,6,7,7,8,8,8-heptafluoro-3,5-octanedione 2,6-Dimethyl-3,5-heptanedione 1,3-Diphenyl-1,3-propanedione Dipivaloylmethane 1,3-Di(2-pyridyl)-1,3-propanedione 3-Ethyl-2,4-pentanedione 2-Furoyltrifluoroacetone 3,5-Heptanedione Hexafluoroacetylacetone 1-(2-Mesitylene)-1,3-butanedione 6-Methyl-2,4-heptanedione 3-Methyl-2,4-pentanedione 1-Phenyl-1,3-butanedione 3-Phenyl-2,4-pentanedione 9H,9H-Triacontafluoro-8,10-heptadecanedione Trifluoroacetylacetone 4,4,4-Trifluoro-1-(2-naphthyl)-1,3-butanedione 4,4,4-Trifluoro-1-phenyl-1,3-butanedione 4,4,4-Trifluoro-1-(2-thienyl)-1,3-butanedione 4,4,4-Trifluoro-1-(p-tolyl)-1,3-butanedione

Unit Size

B2652

Salen Ligands

OH

(CH3)3C

25g

5g

B2653

N

C(CH3)3

(CH3)3C

OH

C(CH3)3 (CH3)3C

B2619

B3015 H3C CH3 H3C CH3 N N

(CH3)3C (CH3)3C

C(CH3)3

HO

CH

N

OH HO

OH

OH

N

N HO

C(CH3)3

D2572

NCH2CH2N

CH HO

CH3

C CH3

OH CH3

HO

C CH3

C CH3 CH3

C CH3

CH3

CH3

CH3

D1307

CH N OH

N

CH3 CH3

C(CH3)3 (CH3)3C

H0199

N

OH HO

B4418

N

N HO

25mL 500mL 10mL 25mL 25mL 5g 25g 5mL 25g 100g 25g 25g 500g 5g 5g 25g 25g 500g 5g 25g 1g 5g 5mL 5g 25g 5g 25g 5g 25g 5g 25g 5mL 5mL 25mL 100g 500g 1g 5g 100mg 25g 100g 10g 25g 25g 25g 500g 5g 25g

Materials Chemistry

Product Name

P0052 A0881 A0869 B1733 B1457 B3382 C1277 D0039 D1729 D2413 D0910 D1678 D2512 E0405 F0083 H1395 H0476 M1272 M0597 M1132 P0160 P1297 T2037 T0434 T1583 T0437 T0438 T2997

Synthetic Organic Chemistry

Product No.

OH

N CH HO

HO

CH3 CH N CH2 CH N CH

C(CH3)3

D1422

OH

HO CH

N

(CH2)3

N CH

Product No.

Product Name

B2652 B2653 B4418 B2619 B3015 H0199

(1R,2R,4R,5R)-2,5-Bis(3,5-di-tert-butyl-2-hydroxybenzylideneamino)bicyclo[2.2.1]heptane (1S,2S,4S,5S)-2,5-Bis(3,5-di-tert-butyl-2-hydroxybenzylideneamino)bicyclo[2.2.1]heptane (R,R)-(-)-N,N '-Bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamine N,N '-Bis(3,5-di-tert-butylsalicylidene)-1,1,2,2-tetramethylethylenediamine N,N '-Bis(5-hydroxysalicylidene)ethylenediamine N,N '-Bis(salicylidene)ethylenediamine

Unit Size 5g 1g 1g 25g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

100mg 100mg 25g 5g 5g 500g

93

Synthetic Organic Chemistry

Ligands

Product No.

Product Name

D2572 D1307 D1422

N,N '-Bis(salicylidene)-1,2-phenylenediamine N,N '-Bis(salicylidene)-1,2-propanediamine N,N '-Bis(salicylidene)-1,3-propanediamine

Unit Size 5g

A1548

A1699

Materials Chemistry

D2521

NH SO2

B2316

F3CO2SHN

NHSO2CF3

D3716

CH3 NH2

CH3

CH3

NH2

CH3

D3719

CH3

D2395

N C CH(C6H5)2

N C CH2C(C6H5)3

N C CH2C(C6H5)3

OH O

OH O

OH O

D2176

N(CH3)2

(CH3)2N

N(CH3)2 OCH3

OCH3

D2175

E0077

NH2

NH2 NH2

H2N

H1215 H N

NH2

H0093

M2476

M2090

H N NH NH

HN

NH

HN

N H

N

. 6HCl

N

NH

N

O CH3(CH2)7

N

O

CH3 O N

N

N

(CH2)7CH3

(CH2)7CH3

(CH2)7CH3

CH3 O N

HO

OH

N H

Q0062

S0884

S0461

N N

H

T1426

. 4HCl

O CH3CH2O C CH2

T1874

H

H

N

N

T2540

HN

OCH3

OCH3 (CH3)2N

NHCH2CH2NH

CH3

NH2

N H

D2396

NH2

HN

H2N

N

N C CH2C(C6H5)3

HN

NHSO2CF3

D0493

CH3

N C CH2C(C6H5)3

HN

CH3

N NH2

N C CH(C6H5)2

H N

NH SO2

CH3

OH O

N H

NH

CH3

CH3 NH2

D3720

D0887

NH

CH3

OH O

H1070

94

CH3

F3CO2SHN

D0134

OH O

D0720

CH3

CH3

B2317

CH3

D2520

NH2

NH2

Amine Ligands

25g 25g 25g

NH

N

NH

H

T1289 O CH2 C OCH2CH3 N N

O N CH2 C OCH2CH3 N O CH2 C OCH2CH3

N CH3

HN

O HO C CH2

N

CH3

N

N

N

O CH2 C OH

N CH2 C OH O

T0548 CH3

CH3

O CH2 C OH N

HN

T0537 CH3

CH3

T1875

N

CH3

CH3

Availability or specification of the listed products are subject to change without prior notice.

CH3

CH3

CH3

N

N

CH3

Ligands

T0147

T1877

CH3

N

N

CH3

N N

CH3

N

T2541

T2642 O

CH3

CH2 C OC(CH3)3

HN

HN

NH

CH3

NH

N

O HO C CH2

H N

H N

N

CH3

T1878

Synthetic Organic Chemistry

CH3

CH3

T1876

O

N

N

CH2 C OC(CH3)3

N CH2 C OC(CH3)3 O

T0429

B4304

T1879

T1243

O CH2 C OC(CH3)3 N HN

O N

CH2 C OC(CH3)3

H2N

N

N H

H N

NH2

CH3

H N

N CH3

H N

CH3 CH3

N

N

CH3

N

H2N H 2N

N

NH2

CH3

CH2 C OC(CH3)3 O

CH3

CH3

N

N

N

CH3

Materials Chemistry

T2898 CH3

N

CH3

CH3

Product No.

Product Name

A1548 A1699 D2520 D2521 B2316 B2317 D0134 D0493 D3716 D3719 D3720 D2395 D2396 D0720 D0887 D2176 D2175 E0077 H1070 H1215 H0093 M2476 M2090 Q0062 S0884 S0461 T1874 T1875 T1426 T2540 T1289 T0537 T0548 T0147 T1877 T1876 T1878 T2642 T2541 T0429

(R,R)-N-(2-Amino-1,2-diphenylethyl)-p-toluenesulfonamide (S,S)-N-(2-Amino-1,2-diphenylethyl)-p-toluenesulfonamide (R,R)-N,N '-Bis(trifluoromethanesulfonyl)-1,2-diphenylethylenediamine (S,S)-N,N '-Bis(trifluoromethanesulfonyl)-1,2-diphenylethylenediamine (1R,2R)-1,2-Bis(2,4,6-trimethylphenyl)ethylenediamine (1S,2S)-1,2-Bis(2,4,6-trimethylphenyl)ethylenediamine 1,4-Diazabicyclo[2.2.2]octane Diethylenetriamine (1S,2S)-N,N '-Dihydroxy-N,N '-bis(diphenylacetyl)cyclohexane-1,2-diamine (1R,2R)-N,N '-Dihydroxy-N,N '-bis(3,3,3-triphenylpropionyl)cyclohexane-1,2-diamine (1S,2S)-N,N '-Dihydroxy-N,N '-bis(3,3,3-triphenylpropionyl)cyclohexane-1,2-diamine (R,R)-(-)-2,3-Dimethoxy-1,4-bis(dimethylamino)butane (S,S)-(+)-2,3-Dimethoxy-1,4-bis(dimethylamino)butane N,N '-Dimethylethylenediamine N,N '-Diphenylethylenediamine (1R,2R)-(+)-1,2-Diphenylethylenediamine (1S,2S)-(-)-1,2-Diphenylethylenediamine Ethylenediamine Anhydrous 1,4,7,10,13,16-Hexaazacyclooctadecane 1,4,7,10,13,16-Hexaazacyclooctadecane Hexahydrochloride Hexamethylenetetramine 2,2'-(Methylimino)bis(N,N-di-n-octylacetamide) N-Methyliminodiacetic Acid Quinuclidine (+)-Sparteine (-)-Sparteine 1,4,7,10-Tetraazacyclododecane 1,4,7,10-Tetraazacyclododecane-1,4,7,10-tetraacetic Acid 1,4,7,10-Tetraazacyclododecane Tetrahydrochloride Tetraethyl 1,4,8,11-Tetraazacyclotetradecane-1,4,8,11-tetraacetate N,N,N ',N '-Tetramethyl-1,4-diaminobutane N,N,N ',N '-Tetramethyl-1,6-diaminohexane N,N,N ',N '-Tetramethyl-1,3-diaminopropane N,N,N ',N '-Tetramethylethylenediamine 1,4,8,11-Tetramethyl-1,4,8,11-tetraazacyclotetradecane 1,5,9-Triazacyclododecane 1,4,7-Triazacyclononane Tri-tert-butyl 1,4,7,10-Tetraazacyclododecane-1,4,7,10-tetraacetate Tri-tert-butyl 1,4,7,10-Tetraazacyclododecane-1,4,7-triacetate Triethylenetetramine

Unit Size

100mg 100mg 25g 100g 25mL

1g 1g 5mL 1g 1g 25mL

25g 1mL 5g 200mg

1g 200mg 1g

25mL 25mL 25mL 200mg 200mg

1g 100mg 25mL

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

1g 1g 1g 1g 500mg 500mg 500g 500mL 100mg 100mg 100mg 5g 5g 25mL 25g 5g 5g 500mL 100mg 100mg 500g 5mL 25g 1g 1g 1g 5g 1g 5g 200mg 25mL 500mL 500mL 500mL 1g 100mg 5g 1g 200mg 500mL

95

Synthetic Organic Chemistry

Ligands

Product No.

Product Name

B4304 T1879 T1243 T2898

N,N ',N ''-Trimethyldiethylenetriamine 1,4,7-Trimethyl-1,4,7-triazacyclononane (stabilized with NaHCO3) Tris(2-aminoethyl)amine Tris[2-(dimethylamino)ethyl]amine

Unit Size

A0261

5mL 1g 5g 25mL 100mL 1g 5g

B3197

B4196 CH3

CH3

R H2N

NH2

Imine Ligands

CH

N

CH2CH2

N

CH

R

Fe

CH

N R=

Fe

CH3 CH3

O

O N

O

CH3

Materials Chemistry

D4273

D4168

D4652

D3822 CH3

N

N

H2N

S

O

N

S

NH2

S

N

O

Br

N

CH3

I0001 N

D2823 O

C

N

N

O

O

F

N

F

N

NH

FF

HN

F

N CH2

CH3CH2

FF F

CH2CH3

A5019

CH3CH2

C(CH3)3

FF

F

FF

O N

CH2CH3

NH

N

N

F

F

T1495

T1438

T1815 HO Cl

NH N

Cl NH

OR

N HN

HO

N

N

T1497

CH3O

OCH3

NH

NH

N

N HN

OH

CH3O

NH N N HN

OCH3

CH3O

OCH3

OCH3

F

F

F

F

F

F

OCH3

N

N HN

F

CH3

F CH3 H3C

F NH

F OH

OH

T1729 F F

HO

N HN CH3O

96

T1730 OCH3

OCH3

N

OH

Cl HO

T1360 OH

OH

N

HO

Cl Cl

OR

CH3O

NH

N HN

HN

Cl

R = CH2CO2H

OH

Cl

Cl

RO

CH N

T1832

N

HN N

OH

CH N

HO CH

N N

OR

HS

N

OH

N

N

FF F

O N

S0328

O N

O

N

P1795 P0355

F

S0267 OH

C(CH3)3

S

O

F F

N HN

FF

CH2CH3

N

M1402 O

N

F

NH N

F

CH3CH2

F

F F

CH2CH3

CH3CH2

C(CH3)3

M1401

P1947

CH2CH3

O

N

C(CH3)3

O N

O0319

CH3CH2

N

CH3

C

O

CH3

C

S

O0234

CH3 O

N

N H

N

N

CH3

C

O

M1390 CH3

CH3

F

I0567 CH3

OH

I0582 CH3

OH CH N

I0795

O

S

CH3

CH3

H0291 OH

CH3

CH3 CH3

Fe PPh2 O

Br

N

CH

N

CH3

CH3

H0973

CH3

F0893

CH3

N

N

OH

N

F

F

F

F

F

F F

F

Availability or specification of the listed products are subject to change without prior notice.

CH3 H3C CH3

CH3 CH3

NH N N HN

CH3 CH3

CH3

CH3

Ligands

T1358

T1359

T2222

T0830

T2993 N

N

N

NH N

HN

N

NH N

HN

N

N

N N

HN

N

N

N NH

Synthetic Organic Chemistry

N

N H

N

N

N N

N N

N

S N

Product Name

A0261 B3197 B4196 D4273 D4168

N,N '-Bis(2-aminobenzal)ethylenediamine 1g (S,S '')-2,2''-Bis[(S)-4-isopropyloxazolin-2-yl]-1,1''-biferrocene 100mg 500mg 20mg (S,S)-4,6-Bis(4-isopropyl-2-oxazolin-2-yl)-m-xylene 2,2'-Diamino-4,4'-bithiazole 200mg 1g 2,4-Dibromo-6-[[[[(4S,5S)-4,5-dihydro-4,5-diphenyl-1-tosyl-1H-imidazol-2-yl]methyl]50mg [(S)-1-phenylethyl]amino]methyl]phenol trans-2,6-Diisopropyl-N-(2-pyridylmethylene)aniline 200mg 1g (S)-1-(Diphenylphosphino)-2-[(S)-4-isopropyloxazolin-2-yl]ferrocene 200mg 1g 4-Fluoro-N-salicylideneaniline 1g 5g 2-(2-Hydroxyphenyl)benzothiazole 5g 25g 2-(2-Hydroxyphenyl)benzoxazole 1g 25g Imidazole 25g 100g 500g 100mg (R,R)-(+)-2,2'-Isopropylidenebis(4-tert-butyl-2-oxazoline) (S,S)-(-)-2,2'-Isopropylidenebis(4-tert-butyl-2-oxazoline) 100mg 1g 250mg 1g 5g (R,R)-2,2'-Isopropylidenebis(4-phenyl-2-oxazoline) (S,S)-2,2'-Isopropylidenebis(4-phenyl-2-oxazoline) 250mg 1g 2,2'-Methylenebisbenzothiazole 5g 25g (+)-2,2'-Methylenebis[(3aR,8aS)-3a,8a-dihydro-8H-indeno[1,2-d]oxazole] 100mg 500mg (-)-2,2'-Methylenebis[(3aS,8aR)-3a,8a-dihydro-8H-indeno[1,2-d]oxazole] 100mg 500mg 2,3,7,8,12,13,17,18-Octaethylporphyrin 100mg 1g 2,3,7,8,12,13,17,18-Octafluoro-5,10,15,20-tetrakis(pentafluorophenyl)porphyrin 100mg 200mg 1g (4S,4'S)-2,2'-(Pentane-3,3'-diyl)bis(4-benzyl-4,5-dihydrooxazole) Phthalocyanine (purified by sublimation) 1g Phthalocyanine 25g 2-Salicylideneaminophenol 5g 25g Salicylideneamino-2-thiophenol 1g 5g N-Salicylideneaniline 25g 5,10,15,20-Tetrakis(4-carboxymethyloxyphenyl)porphyrin 100mg 5,10,15,20-Tetrakis(2,6-dichlorophenyl)porphyrin 100mg 5,10,15,20-Tetrakis(3,5-dihydroxyphenyl)porphyrin 100mg 1g 5,10,15,20-Tetrakis(3,5-dimethoxyphenyl)porphyrin 100mg 5,10,15,20-Tetrakis(4-hydroxyphenyl)porphyrin 100mg 5,10,15,20-Tetrakis(4-methoxyphenyl)porphyrin 100mg 1g 5,10,15,20-Tetrakis(pentafluorophenyl)porphyrin 100mg 5,10,15,20-Tetrakis(2,4,6-trimethylphenyl)porphyrin 100mg 1g meso-Tetraphenylchlorin 100mg Tetraphenylporphyrin (Chlorin free) 1g 5,10,15,20-Tetra(4-pyridyl)porphyrin 1g 2-(4-Thiazolyl)benzimidazole 25g 250g 1g 5g Tris[(1-benzyl-1H-1,2,3-triazol-4-yl)methyl]amine

D4652 D3822 F0893 H0973 H0291 I0001 I0795 I0567 D2823 I0582 M1390 M1401 M1402 O0234 O0319 P1947 P1795 P0355 S0328 A5019 S0267 T1495 T1438 T1815 T1832 T1497 T1360 T1730 T1729 T1358 T1359 T2222 T0830 T2993

Unit Size

B3510

N

Pyridine Ligands

B2217

N H

B2218

O

O

N N

B3934

N N

O

CH3

CH3

CH3

CH3

CH3

O

N HN

O

N NH

O

N N

N

B2220

O O

N CH3

N NH

B2219

CH3

CH3

B4228

N

N H

B4227

O

N

N N

Materials Chemistry

Product No.

O

N N

N

O

O

N N

N

HN CH3

CH3

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

97

Ligands

Synthetic Organic Chemistry

B4104

D4652

D2037 CH3

N

O

CH3

N

N

N

L0065 CH3

N H

N

CH3

L0085

L0063

N

N

L0067

N N

CH3

CH3

T1487

O

CH3

P2100

CH2

N

N

N N CH2

CH3

CH3 N

N

T2671 CH2

CH2 N N

N CH2CH2 N

CH3

L0068

CH3 N

N

N

CH3

CH3

P2098

N

L0066

CH3

N

CH3

N N

N

CH3 C CH3 CH3

Materials Chemistry

D3640

CH3

N

N N

N

CH2

N H

N CH2

N

N

CH2

Product No.

Product Name

B3510 B3934 B4228 B2217 B2218 B4227 B2219 B2220 B4104 D4652 D2037 D3640 L0063 L0085 L0065 L0067 L0066 L0068 P2098 T1487 P2100 T2671

2,6-Bis(2-benzimidazolyl)pyridine 2,6-Bis[(2R,4S,5S)-1-benzyl-4,5-diphenylimidazolidin-2-yl]pyridine 2,6-Bis[(2S,5S)-4,4-diphenyl-1-aza-3-oxabicyclo[3.3.0]octan-2-yl]pyridine (R,R)-2,6-Bis(4-isopropyl-2-oxazolin-2-yl)pyridine (S,S)-2,6-Bis(4-isopropyl-2-oxazolin-2-yl)pyridine 2,6-Bis[(2S,4S)-4-methyl-5,5-diphenyloxazolidin-2-yl]pyridine (R,R)-2,6-Bis(4-phenyl-2-oxazolin-2-yl)pyridine (S,S)-2,6-Bis(4-phenyl-2-oxazolin-2-yl)pyridine (S)-4-tert-Butyl-2-(2-pyridyl)oxazoline trans-2,6-Diisopropyl-N-(2-pyridylmethylene)aniline 3,5-Di(2-pyridyl)pyrazole 3,6-Di(2-pyridyl)-1,2,4,5-tetrazine 2,3-Lutidine 2,4-Lutidine 2,5-Lutidine 2,6-Lutidine 3,4-Lutidine 3,5-Lutidine 2-(2-Pyridyl)benzoxazole N,N,N ',N '-Tetrakis(2-pyridylmethyl)ethylenediamine 2-(1H-1,2,4-Triazol-3-yl)pyridine Tris(2-pyridylmethyl)amine

Unit Size

B1077 KO

1g

250mg

250mg 250mg 1g 200mg 1g 1g

5mL

B4509 O

C

C OK

25mL 25mL 25mL 25mL 25mL 1g 1g 200mg 1g

B0841 O

O

1g 500mg

5g 50mg 50mg 5g 5g 50mg 1g 1g 5g 1g 5g 5g 25mL 500mL 500mL 500mL 500mL 500mL 5g 5g 1g 5g

O

NaO C

C ONa

CH3

CH3

N

N

N

Bipyridine & Terpyridine Ligands N

B1423

B4297

. xH2O

N

N

. xH2O

B4557

B3622

B1876 O

O O N

N

N

N

N

N N

N

HO C C OH N

N

C OH

CN N

98

O

HO C

N

N

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

N

Ligands

B3502

B3533

B3859

B2496

O

HO C

C OH N

O

O N

HO C

N

B0470

N

C OH

B3572

N

N

B4645 CH2Cl

N

N

O

O

B4420

CH2Cl

CH3(CH2)5

N

ClCH2

N

N

(CH2)5CH3

CH2Cl

B4114

N

N

B3732

CH2OH

CH2OH

N

N

B3218 Br

O

N N

N

S

N

B3297 CH3

N

Materials Chemistry

B3973

N

N

B3511

S

N

N

Synthetic Organic Chemistry

O

B0468

CH3

CH3

N

N

N

N H

N

N

CH3

N

N

Br

N

Br N

B3219

D2892 Br

N

N

N

D3988

D2913 NH2

NH2

N

N

H2N

D3134

D3919

N

N

NH2

D4541

N

N

Br

D4635

N

Br

Br

N

N

O

O

CH3O C

C OCH3

N

N

H1347

CH3

CH3

N

N

CH2OH

N

N

OCH2CH3

N

N

B0842

CH3 N

P2202

N

N

(CH2)8CH3 (CH2)8CH3

CH3

N

N

CH3

T0024

N

N

T2959 O

C OCH3

N

OCH3

N

O

N

OCH3

D3917

CH3 N

N

OCH2CH3

CN

B2138

M2464

CH3

N

N

B0852

N

D3886 P

N

Br

Br

D4511 O

NC

N

N

D4358

C(CH3)3 C(CH3)3

Br

N

O

O

C OCH3 C OCH3 C OCH3

N

N

N N

Product No.

Product Name

B1077 B4509 B0841 B1423 B4297 B4557

2,2'-Bicinchoninic Acid Dipotassium Salt Hydrate Bicinchoninic Acid Disodium Salt Hydrate 2,2'-Bi-4-lepidine 2,2'-Bi(1,8-naphthyridine) 2,2'-Bipyrazine 2,2'-Bipyridine-6-carbonitrile

N

N

N N

N

N

Unit Size 1g 1g

5g 5g 100mg 100mg 100mg 200mg 1g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

99

Materials Chemistry

Synthetic Organic Chemistry

Ligands

Product No.

Product Name

B3622 B1876 B3502 B3533 B0468 B3859 B2496 B0470 B3572 B4645 B4420 B3511 B3973 B3297 B4114 B3732 B3218 B3219 D2892 D2913 D3919 D4358 D3988 D3134 D4541 D4511 D3886 D4635 B0852 B2138 B0842 D3917 H1347 M2464 P2202 T0024 T2959

2,2'-Bipyridine-3,3'-dicarboxylic Acid 2,2'-Bipyridine-4,4'-dicarboxylic Acid 2,2'-Bipyridine-5,5'-dicarboxylic Acid 2,2'-Bipyridine-6,6'-dicarboxylic Acid 2,2'-Bipyridyl 2,2'-Bipyridyl 1,1'-Dioxide 2,2'-Bipyrimidyl 2,2'-Biquinoline 4,4'-Bis(chloromethyl)-2,2'-bipyridyl 6,6'-Bis(chloromethyl)-2,2'-bipyridyl 4,4'-Bis(5-hexyl-2-thienyl)-2,2'-bipyridyl 4,4'-Bis(hydroxymethyl)-2,2'-bipyridine 1,2-Bis(4'-methyl-2,2'-bipyridin-4-yl)ethane 2,6-Bis(2-pyridyl)-4(1H)-pyridone 6-Bromo-2,2'-bipyridyl 6-Bromo-4,4'-dimethyl-2,2'-bipyridyl 4'-(4-Bromophenyl)-2,2':6',2''-terpyridine 4'-Bromo-2,2':6',2''-terpyridine 4,4'-Diamino-2,2'-bipyridyl 6,6'-Diamino-2,2'-bipyridyl 4,4'-Dibromo-2,2'-bipyridyl 5,5'-Dibromo-2,2'-bipyridyl 6,6'-Dibromo-2,2'-bipyridyl 4,4'-Di-tert-butyl-2,2'-bipyridyl 6,6'-Dicyano-2,2'-bipyridyl Diethyl 2,2':6',2''-Terpyridine-4'-phosphonate 4,4'-Dimethoxy-2,2'-bipyridyl Dimethyl 2,2'-Bipyridine-4,4'-dicarboxylate 4,4'-Dimethyl-2,2'-bipyridyl 5,5'-Dimethyl-2,2'-bipyridyl 6,6'-Dimethyl-2,2'-bipyridyl 4,4'-Dinonyl-2,2'-bipyridyl 4-Hydroxymethyl-4'-methyl-2,2'-bipyridyl Methyl 2,2':6',2''-Terpyridine-4'-carboxylate 4'-(4-Pyridyl)-2,2':6',2''-terpyridine 2,2':6',2''-Terpyridine Trimethyl 2,2':6',2''-Terpyridine-4,4',4''-tricarboxylate

Unit Size 1g 100mg 1g 100g

25g

200mg 1g 200mg 1g 200mg 1g 1g 1g 1g 200mg 1g 1g 1g

1g 1g 1g 5g 1g 5g 100mg 1g 1g 200mg

100mg

B2695 D0905

B2694 D0711

B0989 NaO3S

SO3Na

Phenanthroline Ligands

. xH2O N

N

N

B0429

C1560

D2565

C0786

Cl

D4421

(CH2)3CH3

D3869

Cl N Cl

100

OH

. xH2O

N Cl

N

N

Br

D0772

HO

Cl

Br

N

N

D4186

N

N

N

N

N CH3(CH2)3

D3209 N

N

. H2O

N N

N

N

Cl

Br

Br

N

N

CH3

CH3

B2632

5g 1g 1g 5g 500g 5g 1g 5g 1g 1g 200mg 5g 1g 1g 5g 5g 5g 5g 1g 250mg 5g 1g 5g 5g 1g 200mg 5g 5g 25g 25g 5g 5g 1g 100mg 200mg 1g 200mg

N

N N

N CH3

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

CH3

Ligands

D1559

D3849

B0985 SO3Na

NaO3S

N N

N0423

CH3

N

N

CH3

N

. HCl . H2O

N

. 1/2H2O

N NO2

. xH2O

O

O

N

N

. H2O

T0847 Br

N

Br N Br

Br N

N

Materials Chemistry

T3133

N

N

CH3

P1973

P0221 P0879

CH3

N

CH3

CH3

N0214

CH3

N

N

N

CH3

D0771

N N

N N

N

M0300

Synthetic Organic Chemistry

CH3

CH3

M2512

CH3 CH3

CH3 CH3

Product No.

Product Name

B2694 D0711 B2695 D0905 B0989 B2632 B0429 C1560 C0786 D3209 D2565 D4186 D4421 D3869 D0772 D1559 D3849 B0985 M2512 M0300 D0771 N0423 N0214 P0221 P0879 P1973 T3133 T0847

Bathocuproine (purified by sublimation) Bathocuproine Bathophenanthroline (purified by sublimation) Bathophenanthroline Bathophenanthrolinedisulfonic Acid Disodium Salt Hydrate 3-Bromo-1,10-phenanthroline 5-Bromo-1,10-phenanthroline Monohydrate 2-Chloro-1,10-phenanthroline 5-Chloro-1,10-phenanthroline 3,8-Dibromo-1,10-phenanthroline 2,9-Dibutyl-1,10-phenanthroline 2,9-Dichloro-1,10-phenanthroline 4,7-Dichloro-1,10-phenanthroline Hydrate 4,7-Dihydroxy-1,10-phenanthroline 4,7-Dimethyl-1,10-phenanthroline 5,6-Dimethyl-1,10-phenanthroline 2,9-Diphenyl-1,10-phenanthroline Disodium Bathocuproinedisulfonate 2-Methyl-1,10-phenanthroline 5-Methyl-1,10-phenanthroline Hydrate Neocuproine Hemihydrate Neocuproine Hydrochloride Monohydrate 5-Nitro-1,10-phenanthroline 1,10-Phenanthroline Monohydrate 1,10-Phenanthroline Monohydrate 1,10-Phenanthroline-5,6-dione 3,5,6,8-Tetrabromo-1,10-phenanthroline 3,4,7,8-Tetramethyl-1,10-phenanthroline

Unit Size 1g 1g 1g

200mg 100mg 100mg 200mg 100mg 200mg 200mg

100mg 100mg 100mg 1g 1g 5g 1g 1g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

5g 5g 1g 5g 1g 200mg 1g 1g 1g 1g 1g 1g 1g 1g 100mg 1g 1g 1g 1g 1g 25g 25g 1g 25g 25g 5g 100mg 1g

101

Asymmetric Organocatalysts Eder . and Hajos . separately reported an intramolecular asymmetric aldol reaction which employed proline as the only asymmetric catalyst at the beginning of the 1970s.1) This reaction was considered to be a special case at that time. Later in 2000, List . reported an intermolecular asymmetric aldol reaction which used proline as a catalyst.2) List’ s report received broad attention and served as a trigger to make research active for asymmetric organic catalysts. Therefore, varieties of asymmetric organic catalysts have been developed and the research has been applied to many areas.3) The proline derivative 1, having the heterocyclic ring was developed by Nakamura . It shows high TON as an asymmetric catalyst for obtaining a chiral aldol adduct.4) O

Br

Materials Chemistry

Synthetic Organic Chemistry

Asymmetric Organocatalysts

N H

O Br

N H

Br

C NH S

S 1 O O . CF3CO2H (0.5 mol%)

HO

O

Br

Acetone, H2O

N H

O

O

Y. 70%, 92% e.e.

Compared with conventional metal complex catalysts, asymmetric organic catalysts are considered to be environmentally friendly and are expected to be further developed because they are stable, easy to handle and free of harmful metals.

A1301

A0945

A1043 O

Prolines and Their Analogs

N

CH2NH2

CH2CH3

B3440

D3803

H3C

D3804

N H

H3C C Si O

N H

NH

D3185

D3186

N H

N H

O

H3C N H

D2365

D2735

F0818 OH

C

N H

H1407

H0784 OH

F

C N H

H0768

N H

C OH

OH N H

OH

CH2NH

I0589

OH

H N

N H

OH

C

CH3

O

O

CH3

I0395

N

CH3

M1169

M1161

OH N CH3

102

C N H

OH O

N H

OH O

N H

CH2OCH3

N H

CH2OCH3

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

Asymmetric Organocatalysts

M1097

CH2NH

M2077

N

CH3

CH2 N

N H

CH3

P1830

P1404

O

C OH

P1784

CH2 N

O

OH

T3080 N

N H

N H

N

C OH

OH O

N H

CH2 N

T0219

O N H

N H H

CH3

P1925

N H

O

O

N

. 2HCl P0481

N H

C OH

N N H

H N

O

O

C NH S O

Materials Chemistry

P1241

N H

O0370

CH3 OH

P0994

O N H

M1995

Synthetic Organic Chemistry

N

M1183

HO C

NH

S S

Product No.

Product Name

A1301 A0945 A1043 B3440 D3803 D3804 D3185 D3186 D2365 D2735 F0818 H1407 H0784 H0768 I0589 I0395 M1169 M1161 M1097 M1183 M2077 M1995 O0370 P1830 P1404 P0994 P0481 P1925 P1241 P1784 T3080 T0219

(S)-(-)-2-Aminomethyl-1-ethylpyrrolidine (S)-(+)-2-(Anilinomethyl)pyrrolidine L-Azetidine-2-carboxylic Acid trans-4-(tert-Butyldiphenylsilyloxy)-L-proline (R)-(+)-2-(Diphenylmethyl)pyrrolidine (S)-(-)-2-(Diphenylmethyl)pyrrolidine (2R,5R)-2,5-Diphenylpyrrolidine (2S,5S)-2,5-Diphenylpyrrolidine (R)-(+)-α,α-Diphenyl-2-pyrrolidinemethanol (S)-(-)-α,α-Diphenyl-2-pyrrolidinemethanol trans-4-Fluoro-L-proline (2S)-N-[(1S)-1-(Hydroxydiphenylmethyl)-3-methylbutyl]-2-pyrrolidinecarboxamide (R)-(-)-2-[Hydroxy(diphenyl)methyl]-1-methylpyrrolidine (S)-(+)-2-[Hydroxy(diphenyl)methyl]-1-methylpyrrolidine (R)-(+)-Indoline-2-carboxylic Acid (S)-(-)-Indoline-2-carboxylic Acid (R)-2-(Methoxymethyl)pyrrolidine (S)-2-(Methoxymethyl)pyrrolidine (S)-(-)-1-Methyl-2-(1-naphthylaminomethyl)pyrrolidine (S)-(-)-1-Methyl-2-(1-piperidinomethyl)pyrrolidine α-Methyl-L-proline (S)-2-[(1-Methyl-2-pyrrolidinyl)methyl]isoindoline Dihydrochloride (2S,3aS,7aS)-Octahydro-1H-indole-2-carboxylic Acid D-Pipecolic Acid L-Pipecolic Acid D-Proline L-Proline (R)-(-)-1-(2-Pyrrolidinylmethyl)pyrrolidine (S)-(+)-1-(2-Pyrrolidinylmethyl)pyrrolidine (S)-5-(Pyrrolidin-2-yl)-1H-tetrazole N-(2-Thiophenesulfonyl)-L-prolinamide L-Thioproline

Unit Size 1g 1g 100mg 1g

1g 1g 200mg 1g 100mg 1g 1g 1g 1g 1g 1g 1g 1g 5g 1g 5g 25g 1g 100mg 25g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

5g 5g 1g 5g 1g 1g 100mg 100mg 5g 5g 50mg 1g 5g 5g 1g 5g 5g 5g 1g 5g 5g 5g 5g 25g 5g 25g 250g 1g 5g 500mg 100mg 500g

103

Asymmetric Organocatalysts

Synthetic Organic Chemistry

A0177

B3398 O

O CH3

Other Amino Acids

M0102

M0099

OH

CH3

CH3

OH

Product Name

A0177 A0179 B3398 M0102 M0099 P0135 P0134 T2937 T0228 T0230 T0539 T0541

D-Alanine L-Alanine

OH

OH

PPh2

NH2

N H

HO

Cinchona Alkaloids

H

H

CH2

B1684

HO

CH2

CH2

H

Cl

HO

H

CH2

H

CH3O N

N

CH2 CH

H

CH

N

C0349

H

CH2

Cl N

N

C0348 CH2 CH

H

CH

N

C0347

25g 250g 5g 25g 500g 25g 250g 100mg 25g 500g 100g 500g 5g 25g 25g

25g

B1689 CH

5g 25g 1g 5g 100g 5g 25g

1g 25g

Cl

H

C0350 CH2 CH

H

CH2

CH

H

Cl H

HO

N

HO

N

N

C0351

H

N

H

N

. HCl . xH2O

N

H N O N

N

N

H

N

H0752

I0728 CH3CH2

N

HO

. 2H2SO4 . 2H2O

CH2

N

N

H

N

D4305

CH2

H

HO

N

D4306 CH

HO

104

HO

. 2HCl

N

CH2

H

CH2

CH3O

CH3

Unit Size

CH2

CH

Ph

CH3 CH3

OH

NH2

N H

B1683

CH2

Ph

O

O-tert-Butyl-L-threonine D-Methionine L-Methionine D-Phenylalanine L-Phenylalanine O-TBDPS-D-Thr-N-Boc-L-tert-Leu-Diphenylphosphine D-(+)-Threonine L-(-)-Threonine D-Tryptophan L-Tryptophan

B1685

NH

(CH3)3CO

Si

O

O

NH2

NH2

Product No.

NH2

O

N H

CH3

T0541

O

OH

OH

NH2

CH3 CH3 O

CH3

OH

T0539

O

OH

T2937 O

OH

T0230

OH NH2

O

NH2

T0228

CH3

P0134

O CH3S

OH NH2

P0135

O CH3S

O

(CH3)3CO

CH3

OH NH2

NH2

Materials Chemistry

A0179

CH3CH2

H

N

H N

N

N HO

O

CH3O

N

O

H

. HCl

H

HO

N

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

N

Asymmetric Organocatalysts

Q0076

Q0074

Q0010 H

Q0028

CH2 CH

N

N

N

HO

N HO

H

CH3O

CH2OH

CH2 CH

H

CH3O N

2

N

H

HO

H

. H2SO4 . 2H2O

H

Synthetic Organic Chemistry

CH2 CH

CH2 CH

CH2 CH

HOCH2

Q0006

N

CH3O N

Q0030 CH2

HO

H

CH

H

N

. HCl . 2H2O

CH3O N

Product Name

B1683 B1689 B1684 B1685 C0347 C0348 C0349 C0350 C0351 D4306 D4305 H0752 I0728 Q0076 Q0074 Q0006 Q0010 Q0028 Q0030

N-Benzylcinchonidinium Chloride N-Benzylcinchoninium Chloride N-Benzylquinidinium Chloride N-Benzylquininium Chloride Cinchonidine Cinchonidine Dihydrochloride Cinchonidine Sulfate Dihydrate Cinchonine Cinchonine Hydrochloride Hydrate N-(9-Deoxy-epi-cinchonidin-9-yl)picolinamide N-(9-Deoxy-epi-cinchonin-9-yl)picolinamide Hydroquinidine Hydrochloride β-Isocupreidine Quincoridine Quincorine Quinidine Quinidine Sulfate Dihydrate Quinine Quinine Hydrochloride Dihydrate

Unit Size

25g

25g 100mg 100mg 5g 5g 25g

B1144

O

Chiral Phosphoric Acids

10g 5g 5g 5g 250g 25g 25g 200g 25g 100mg 100mg 250g 1g 1g 1g 25g 25g 100g 25g

25g

B1143

O

Product No.

Product Name

B1143 B1144

(R)-(-)-1,1'-Binaphthyl-2,2'-diyl Hydrogen Phosphate (S)-(+)-1,1'-Binaphthyl-2,2'-diyl Hydrogen Phosphate

O

O

P OH

O

O P OH

Unit Size 100mg

B1142

Chiral Diols

Materials Chemistry

Product No.

B1100

1g 100mg

5g 1g

B2048

OH

OH

OH

OH

OH

HO

O

O

H3C CH3

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

105

Asymmetric Organocatalysts

Synthetic Organic Chemistry

B1614

B1615 OH

HO

O

O

OH

HO

O

O

H3 C

H3C CH3

Product No.

Product Name

B1142 B1100 B2048 B1614 B1615

(R)-(+)-1,1'-Bi-2-naphthol (S)-(-)-1,1'-Bi-2-naphthol (+)-4,5-Bis[hydroxy(diphenyl)methyl]-2,2-dimethyl-1,3-dioxolane (-)-4,5-Bis[hydroxy(diphenyl)methyl]-2,2-dimethyl-1,3-dioxolane (+)-4,5-Bis[hydroxy(diphenyl)methyl]-2-methyl-2-phenyl-1,3-dioxolane

Unit Size 5g 5g 1g 1g

25g 25g 5g 5g 1g

Materials Chemistry

Chiral Phase-transfer Catalysts (see p.110)

B3296

B3549

B3592

N

N BF4

Others

S

N

S

N

N

N

CF3

CH3

CH3

N

B3593

C0015

C0972

D3983

D3984 CH3

CH3

BF4

O

N

N

CH3 HO3SCH2

CH3 CH2SO3H

CH3 H

O

N N

CF3

N H

E0974

I0807

L0272

CH2CH3 CH3CH2 CH3

O N

CH3 O O N CH3 H CH3

I

CH3 O O N CH3 H

N H

Cl

. H2O

H

HN

N N

CH3

N Cl

. H2O

O

L0137

CH3

OH CH3

O

H

CH3

H OCH3

O

. HBr

OH

OCH3 OH OH

CH3 CH3

O

N

L0236 OCH3 H

N

CH3

NH2

CH3

OH CH3

NH2

CH3 O

T1215 N N

S

. HCl

Product No.

Product Name

B3296 B3549 B3592

(+)-Benzotetramisole 200mg 1g (-)-Benzotetramisole (R)-Benzyl-2-[4-(trifluoromethyl)phenyl]-6,7-dihydro-5H-pyrrolo[2,1-c][1,2,4]triazolium Tetrafluoroborate 200mg (S)-Benzyl-2-[4-(trifluoromethyl)phenyl]-6,7-dihydro-5H-pyrrolo[2,1-c][1,2,4]triazolium Tetrafluoroborate 200mg

B3593

106

Unit Size

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

5g 1g 1g 1g

Asymmetric Organocatalysts

Product Name

C0015 C0972 D3983

(+)-10-Camphorsulfonic Acid (-)-10-Camphorsulfonic Acid (+)-(5aR,10bS)-5a,10b-Dihydro-2-(2,4,6-trimethylphenyl)-4H,6H-indeno[2,1-b][1,2,4]triazolo[4,3-d][1,4]oxazinium Chloride Monohydrate (-)-(5aS,10bR)-5a,10b-Dihydro-2-(2,4,6-trimethylphenyl)-4H,6H-indeno[2,1-b][1,2,4]triazolo[4,3-d][1,4]oxazinium Chloride Monohydrate (1R,3S,5R,7R,8aS)-7-Ethylhexahydro-1-(6-hydroxy-4-quinolinyl)-3,7-methano1H-pyrrolo[2,1-c][1,4]oxazine (R,R)-2-Iodo-1,3-bis[1-(mesitylcarbamoyl)ethoxy]benzene Lappaconitine Hydrobromide D-(-)-Leucinol L-(+)-Leucinol Levamisole Hydrochloride

D3984 E0974 I0807 L0272 L0236 L0137 T1215

Unit Size 25g

100g 25g

Synthetic Organic Chemistry

Product No.

500g 500g 100mg 100mg

200mg 1g 5mL 10g

100mg 200mg 1g 5g 25mL 25g

References

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

107

Materials Chemistry

1) U. Eder, G. Sauer, R. Wiechert, . 1971, , 496; Z. G. Hajos, D. R. Parrish, . 1974, , 1615. 2) B. List, R. A. Lerner, C. F. Barbas III, . 2000, , 2395. 3) Review: K. N. Houk, B. List, . 2004, , 487-631,“Asymmetric Organocatalysis”(special edition); 2007, H. Pellissier, , 9267; A. Berkessel, H. Gröger, in , Wiley-VCH, Weinheim, 2005. 4) S. Nakamura, N. Hara, H. Nakashima, K. Kubo, N. Shibata, T. Toru, . 2008, , 8079.

Chiral Auxiliaries

Synthetic Organic Chemistry

Chiral Auxiliaries

B1786

B1754

CH2

Chiral Oxazolidinones

Materials Chemistry

B2166

I0761

N

CH3 CH

NH O

O

O

CH3

O

P1307

CH3 CH3

NH

O

O

Product No.

Product Name

B1786 B1754 B2165 B2166 I0761 I0762 I0572 I0451 I0594 I0573 P1307 P1308

(R)-4-Benzyl-2-oxazolidinone (S)-4-Benzyl-2-oxazolidinone (R)-(-)-4-Benzyl-3-propionyl-2-oxazolidinone (S)-(+)-4-Benzyl-3-propionyl-2-oxazolidinone (4R)-(+)-4-Isopropyl-5,5-diphenyl-2-oxazolidinone (4S)-(-)-4-Isopropyl-5,5-diphenyl-2-oxazolidinone (R)-4-Isopropyl-2-oxazolidinone (S)-4-Isopropyl-2-oxazolidinone (R)-(-)-4-Isopropyl-3-propionyl-2-oxazolidinone (S)-(+)-4-Isopropyl-3-propionyl-2-oxazolidinone (R)-(-)-4-Phenyl-2-oxazolidinone (S)-(+)-4-Phenyl-2-oxazolidinone

O

1g 1g

A1535

Others

Ph

N O

CH3 Ph

CH3 CH3

SO2

O

CH3 Ph

SO2 CH3

N Bn

B2048 CH3

CH3

CH3

Ph OH

SO2 CH3

Bn

CH3

Ph

N O

CH3 O

SO2 CH3

SO2

CH3

N Bn

CH3

B1614 OH

HO

O

CH3 O

O

O

H3C CH3

108

CH3

OH

HO

O

O

Ph

N Bn

CH3

Ph

O

P1372 CH3

CH3

CH3 N

O

P1371

25g 25g 25g 5g 5g 5g 25g 25g 5g 5g 25g 25g

B2103 CH3

CH3

SO2

5g 5g 5g 1g 1g 1g 5g 5g 1g 1g 5g 5g

1g

CH3

CH3

O

Unit Size

CH3

CH3

O

NH

O

A1534

CH3

O

O

P1308

CH3

N O

CH3

NH

O

CH3

O

B2104

CH3

NH O

O N

CH3

CH3

NH

O

I0573

CH3

O

I0451

O

I0594

O

O

I0572

C CH2CH3

O

CH3

O

C CH2CH3

N

CH3

CH3 CH

O CH2

CH2

NH

O

I0762 CH3

O

CH2

NH O

B2165

H3C CH3

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

Ph OH

Chiral Auxiliaries

B1615

B2907 HO

O

O

C1324 CH3

O (CH3)3C S NH2

(CH3)3C S NH2

D2898

C2023 C1615 CH3

NH S

S

O

O

D2899

CH3

B Cl CH3 2

CH3

CH3 N C

N CH2OH

H CH2

N CH3

CH3

CH3 N C

CH2OH

CH3

NH

H CH2

S

S

T2579 CH3

CH3 CH3

S

Materials Chemistry

T2578

N

CH3

2

N

O

I0575

CH3 B Cl

CH3

HN O

C1614

CH3

CH3

O

H3C

CH3

C1325

Synthetic Organic Chemistry

OH

B2908

CH3

CH3

S

CH3

Product No.

Product Name

A1534

Acetic Acid (1R,2S)-2-[N-Benzyl-N-(mesitylenesulfonyl)amino]-1-phenylpropyl Ester

A1535

Acetic Acid (1S,2R)-2-[N-Benzyl-N-(mesitylenesulfonyl)amino]-1-phenylpropyl Ester

B2103 B2104 P1371

(1R,2S)-2-[N-Benzyl-N-(mesitylenesulfonyl)amino]-1-phenyl-1-propanol (1S,2R)-2-[N-Benzyl-N-(mesitylenesulfonyl)amino]-1-phenyl-1-propanol (1R,2S)-2-[N-Benzyl-N-(mesitylenesulfonyl)amino]-1-phenylpropyl Propionate

P1372

(1S,2R)-2-[N-Benzyl-N-(mesitylenesulfonyl)amino]-1-phenylpropyl Propionate

B2048 B1614 B1615 B2907 B2908 C1324 C1325 C1614 C2023 C1615 D2898 D2899 I0575 T2578 T2579

(+)-4,5-Bis[hydroxy(diphenyl)methyl]-2,2-dimethyl-1,3-dioxolane (-)-4,5-Bis[hydroxy(diphenyl)methyl]-2,2-dimethyl-1,3-dioxolane (+)-4,5-Bis[hydroxy(diphenyl)methyl]-2-methyl-2-phenyl-1,3-dioxolane (R)-(+)-tert-Butylsulfinamide (S)-(-)-tert-Butylsulfinamide (+)-10,2-Camphorsultam (-)-10,2-Camphorsultam (+)-B-Chlorodiisopinocampheylborane (58% in Hexane, ca. 1.6mol/L) (-)-B-Chlorodiisopinocampheylborane (55-65% in Heptane, ca. 1.7mol/L) (-)-B-Chlorodiisopinocampheylborane (60% in Hexane, ca. 1.7mol/L) (4R,5R)-1,3-Dimethyl-4,5-diphenyl-2-[(S)-1-benzyl-2-hydroxyethylimino]imidazolidine (4S,5S)-1,3-Dimethyl-4,5-diphenyl-2-[(R)-1-benzyl-2-hydroxyethylimino]imidazolidine (S)-4-Isopropylthiazolidine-2-thione (1R,4R,5R)-4,7,7-Trimethyl-6-thiabicyclo[3.2.1]octane (1S,4S,5S)-4,7,7-Trimethyl-6-thiabicyclo[3.2.1]octane

Unit Size 1g

[Reagent for double aldol reaction] [Reagent for double aldol reaction]

1g 1g

1g 5g 5g 1g

[Reagent for anti-selective asymmetric aldol reaction] [Reagent for anti-selective asymmetric aldol reaction]

1g 1g 1g 1g 1g 1g

1g 1g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

1g 5g 5g 1g 5g 5g 5g 5g 100mL 100mL 100mL 100mg 100mg 1g 5g 5g

109

Synthetic Organic Chemistry

Chiral Phase-transfer Catalysts

Chiral Phase-transfer Catalysts A phase-transfer catalyst enables the reaction in a heterogeneous system between general organic compounds soluble in organic solvents and compounds soluble in water such as inorganic salts. The reaction can be accomplished in a biphasic system of an inexpensive nonpolar aprotic solvent and water without using DMSO or DMF which are high-polar solvents. A phase-transfer catalyst is soluble in both solvents, and it carries anions of inorganic salts into organic solvents and returns them into the water phase. Reactions usually progress under mild conditions with easy work-up procedures. For this reason, they are also used industrially. Typical phase-transfer catalysts are quaternary ammonium salts, crown ethers, and phosphonium compounds etc. Reaction examples are shown as follows.1-4) Alkylation

Materials Chemistry

CH3OCH2CHCH3 OH

TBAB

+ BuCl

OBu

50% NaOH aq.

Y. 97%

TBAB : Tetrabutylammonium Bromide

C8H17Cl

Bu3P

+ Na2S

C16H33

1)

CH3OCH2CHCH3

2)

Br

(C8H17)2S

H2O

Y. 91%

Cyanation 3)

Cl(CH2)3Cl

18-Crown-6

+ KCN

NC(CH2)3CN

CH3CN

Y. 97%

Oxidation CH3(CH2)7CH CH2 + KMnO4

4)

(C8H17)3N CH3 Cl

CH3(CH2)7CO2H

Benzene – H2O

Y. 91%

The asymmetric synthesis is realized using optically-active phase-transfer catalysts. The asymmetric synthesis using the cinchona alkaloid derivative as a phase-transfer catalyst was reported in the 1980s.5) Shibasaki . succeeded in the total synthesis of cylindricine C involving the asymmetric Michael addition catalyzed by tartaric acid derivatives.6) In this section, we introduce the cinchona alkaloid derivatives and the tartaric acid derivatives as the asymmetric phase-transfer catalysts. CH2 OH N

Cl

N

O Ph2C N

Ot-Bu

+ BnBr

[B1689] (10 mol%) CH2Cl2 50% NaOH aq. 20 ºC, 9 h

O Ph2C N

5)

Ot-Bu Bn

Y. 75% 66% e.e. (R)

110

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

Chiral Phase-transfer Catalysts

5

N

CO2Bn

O

(S,S)-TaDiAS-2nd* (cat.) [D3476] (10 mol%)

O

+

O

Cs2CO3, PhCl -40 ºC, 66 h

C6H13

5

Ph

BnO2C

O tandem cyclization

N

Ph

Y. 84% 82% e.e.

6)

N C6H13

CH

H

CH2

Cl H

B1684 CH

H

N

N

HO

CH2

N

CH2

Cl

CH

H Cl N

CH2

HO

H

Materials Chemistry

B1689

CH2

HO

(+)-cylindricine C total 6 steps

C6H13

HO

B1683

Cinchona Alkaloid Derivatives

Ph

O

N BnO2C

C6H13

Synthetic Organic Chemistry

O Ph

CH2

H

CH3O N

N

B1685 CH2

CH

H Cl

HO

H

N CH2

CH3O N

Product No.

Product Name

B1683 B1689 B1684 B1685

N-Benzylcinchonidinium Chloride N-Benzylcinchoninium Chloride N-Benzylquinidinium Chloride N-Benzylquininium Chloride

Unit Size 10g 5g 5g 5g

D3475 CH3 CH2Ph CH2 N CH2 O

Tartaric Acid Derivatives

O CH2 N CH2 CH2Ph CH3

D3476

CH3 CH3 2BF4

2

2

CH3 CH2Ph CH2 N CH2 O O CH2 N CH2 CH2Ph CH3

CH3 CH3

2

2

2BF4

Product No.

Product Name

D3475

6,10-Dibenzyl-N,N '-dimethyl-N,N,N ',N '-tetrakis(4-methylbenzyl)-1,4-dioxaspiro[4.5]decane(2R,3R)-diylbis(methylammonium) Tetrafluoroborate [=(R,R)-TaDiAS-2nd] 6,10-Dibenzyl-N,N '-dimethyl-N,N,N ',N '-tetrakis(4-methylbenzyl)-1,4-dioxaspiro[4.5]decane(2S,3S)-diylbis(methylammonium) Tetrafluoroborate [=(S,S)-TaDiAS-2nd]

D3476

Unit Size 200mg

1g

200mg

1g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

111

Chiral Phase-transfer Catalysts

Synthetic Organic Chemistry

References H. H. Freedman, R. A. Dubois, . 1975, , 3251. 1974, 565. D. Landini, F. Rolla, F. L. Cook, C. W. Bowers, C. L. Liotta, . 1974, , 3416. C. M. Starks, . 1971, , 195. M. J. O'Donnell, W. D. Bennett, S. Wu, . 1989, , 2353. T. Shibuguchi, H. Mihara, A. Kuramochi, S. Sakuraba, T. Ohshima, M. Shibasaki, . 2006, , 4635; H. 2007, Mihara, T. Shibuguchi, A. Kuramochi, T. Ohshima, M. Shibasaki, , 421. 7) Review: Phase-Transfer Catalysts M. Makosza, . 2000, , 1399; J. M. McIntosh, . 1978, , 235; 1976, 168; A. C. Knipe, P. Varughese, . 1977, , 666; G. W. Gokel, H. D. Durst, . 1976, 1973, 441. , 618; J. Dockx, 2003, Asymmertic Phase-Transfer Catalysts K. Nagasawa, , 670; K. Maruoka, T. Ooi, . 2003, , 3013.

Materials Chemistry

1) 2) 3) 4) 5) 6)

112

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

Optical Resolving Agents

O PhCH2

C Cl

O PhCH2

NHTs 1 [T1444]

i)

C O NHTs

ii) recrystallization

OH

Y.64% ( >99% d.e.)

40% KOH aq.

OH

On the other hand, it has been reported that optical resolution is achieved by catalytic amount of chiral source. Ishihara and co-workers have studied minimal artificial enzymes to overcome various problems of enzymatic reactions and to use optical resolution. One reagent that has been developed is α-(2,4,6triisopropylbenzenesulfonyl)- -( -butyldimethylsilyl)-π-methyl-L-histidinol (2). They reported that this reagent was a very effective catalyst for kinetic resolution of racemic alcohols by selective acylation2). This reagent can also be used as catalyst for the kinetic resolution of 1,2-diols, β-hydroxycarboxylic acids, and 2-amino alcohols after the suitable derivatization. H3C N

OTBDPS HN

N

SO2

i-Pr

O O C N OH syn, racemic

i-Pr

2 [T2223] (5 mol%)

i-Pr

(i-PrCO)2O (0.5 eq.) i-Pr2NEt (0.5 eq.) nonpolar solvent (49% conv.)

O

O

O C N

O C N

+ O C 94% e.e.

O

i-Pr

OH 90% e.e.

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

113

Materials Chemistry

The optical resolution is the method of separating enantiomers from racemates. There are currently many methods to obtain optically active compounds. These methods include asymmetric synthesis, use of chiral building blocks, and optical resolution. In recent years, there has been rapid improvements in asymmetric synthesis, with many reports of success. Optical resolution is widely used, as it is an easy and practical method. One of the most common optical resolution methods utilizes diastereomer which are obtained from the reaction of racemic compounds and an optical resolving agents. The differences of physical properties between diastereomers are utilized in this method. The optical resolving agents are often easily obtained from natural products. For example, alkaloids are used for the optical resolution of racemic acids and tartaric acid is used for the optical resolution of racemic bases. In both cases, diastereomeric salts are formed. When alcohols are to be resolved, the alcohols are reacted with phthalic anhydride to form half ester. The resulting carboxylic acid (half ester) is often then reacted with alkaloids to form diastereomeric salts, which are then resolved. Recently, Ikegami and co-workers have reported a new resolution method for alcohols using amino acid derivatives.1) According to their report, racemic 1-octyn-3-ol is reacted with ( )- - toluenesulfonylphenylalanyl chloride (1), to produce diastereomeric ester. This diastereomeric ester is recrystallized four times from mixed solution of ethanol and hexane, giving the resolved ester with a theoretical yield of 64% (>99% d.e.). Finally, ( )-1-octyn-3-ol is obtained by hydrolysis of pure diastereomeric ester (>99% e.e.). This method is drawing attention as an easy and accurate way to optically resolve alcohols.

Synthetic Organic Chemistry

Optical Resolving Agents

Synthetic Organic Chemistry

Optical Resolving Agents

Shiina and co-workers developed the kinetic resolution of racemic alcohols and racemic carboxylic acids using 4-methoxybenzoic anhydride (PMBA) (3) and a Birman-type asymmetric catalyst3) [(+)-benzotetramisole, (+)-BTM].4) For example, in the reaction of racemic alcohols with achiral carboxylic acids, first the mixed anhydrides are formed from PMBA and the carboxylic acids. Subsequently the mixed anhydrides and one enantiomer of racemic alcohol react preferentially to form optically active esters and optically active alcohols using catalyst (+)-BTM. If this reaction is performed replacing the reactive substrates with racemic carboxylic acids and achiral alcohols, the kinetic resolution proceeds efficiently and optically active esters and optically active carboxylic acids can be obtained. The optical resolution of an anti-inflammatory agent, ibuprofen, has been achieved as an example of this reaction. O

O O

O OH

Materials Chemistry

R1

CH3O

+ R2CO2H

3 [M1973]

R2

O

OCH3

R1

OH R1

+

(+)-BTM (cat.), iPr2NEt, CH2Cl2, rt

[B3296]

O OH

O

3 [M1973]

+ R3OH

(+)-BTM (cat.),

iPr

2NEt,

[B3296]

CH3

O

+

3

OR

CH2Cl2, rt

OH

CH3

CH3

BTM=(+)-Benzotetramisole

A1230

A1231

A1017 OH

NH2

NH2

for Resolution of Acids

OH OH

OH

A1029

A0526

NH H2N

O

N H

NH OH H2N

O

B1118

CH3O N

H

C0349 CH2 CH

HO

H

H

N

C0350 CH2 CH

HO

H

. 2HCl N

114

H

H

CH

CH2 CH

H CH3O

N

H

O

O

HO

HO

H

N

H

N

H H

O

. HCl . H2O

CH2

H

N

N

C0791 CH

H CH2

CH

N

N

N

. 2H2SO4 . 2H2O N

CH2

CH3O

C0351 H

N

C0347

H

O

C0348

S

H N

CH3O

NHCH2

N N

B0671

H

NHCH2

S

. HCl

NH2

H

CH2OH

N OH

B0946 B0670

CH2OH

B3549

O

N H

NH2

O2N

B3296

NH

OH H2N

N H

NH2

B1119

A0528

NH2

HO

H

N

H

N HO

. HCl . xH2O

. H2SO4 . 2H2O

H

N

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

2

Optical Resolving Agents

D1588

H0752

L0129 CH3CH2

H

CH3O

H

O

N HO

CH3

H2N

O

OH

O

H2N

H2N

OH

M0826

M0545

N0543

CH3

N0482

CH3

CH3

NH2

CH3

O H2N

OH

OH

. HCl

NH2

CH3

CH3

P1289 CH3

. HCl

OH

CH3

NO2

CH3

P1028

P0794

Q0006

Q0010 H

Q0028

CH2 CH

NH2

N HO

H

CH3O

N O

O

H

O

. HCl . xH2O

N

HO

N

H

H

N

. HCl . 2H2O

N

N

T1380 CH3

N

NH2

H N

H H

H

CH3O

N

O

CH

CH2

CH3O

H H

H

H

H

S0094

H

H

H

. H2SO4 . 2H2O

S0093 N

N

H

2

N

S0257

H

HO

H

CH3O N

S0249

NH2

Q0030 CH2 CH

H

N HO

CH3

NH2

NH2

CH2 CH

NH2

OH

OH

CH3

P0793 CH3

NH2

P1118

NH2

Materials Chemistry

N0481

O

. HCl

NH2

N

L0071

N

OH

. 2HCl

NH2

NH2

. HCl

NH2

L0128

H

CH3

CH3

L0131

Synthetic Organic Chemistry

CH3

O

. HNO3

O

H

H H

O

2

CH3

. H2SO4 . 5H2O

T1381 CH3

NH2

CH3

Product No.

Product Name

A1230 A1231 A1017 A1029 A0526 A0528 B3296 B3549 B1119 B1118 B0946 B0670 B0671 C0347

(1R,2S)-(-)-2-Amino-1,2-diphenylethanol (1S,2R)-(+)-2-Amino-1,2-diphenylethanol D-(-)-threo-2-Amino-1-(4-nitrophenyl)-1,3-propanediol D-(-)-Arginine L-(+)-Arginine L-(+)-Arginine Hydrochloride (+)-Benzotetramisole (-)-Benzotetramisole (+)-cis-2-Benzylaminocyclohexanemethanol (-)-cis-2-Benzylaminocyclohexanemethanol Brucine Anhydrous Brucine Hydrate Brucine Hydrochloride Monohydrate Cinchonidine

Unit Size

25g 200mg

1g 1g 25g 1g 100g 25g 1g 1g 1g

25g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

5g 5g 500g 5g 500g 500g 5g 1g 5g 5g 25g 25g 5g 250g

115

Materials Chemistry

Synthetic Organic Chemistry

Optical Resolving Agents

Product No.

Product Name

C0348 C0349 C0350 C0351 C0791 D1588 H0752 L0129 L0131 L0128 L0071 M0826 M0545 N0543 N0482 N0481 P1289 P1028 P0794 P0793 P1118 Q0006 Q0010 Q0028 Q0030 S0249 S0257 S0093 S0094 T1380 T1381

Cinchonidine Dihydrochloride Cinchonidine Sulfate Dihydrate Cinchonine Cinchonine Hydrochloride Hydrate Cinchonine Sulfate Dihydrate (+)-Dehydroabietylamine Hydroquinidine Hydrochloride L-(+)-Lysine L-(+)-Lysine Dihydrochloride D-(-)-Lysine Monohydrochloride L-(+)-Lysine Monohydrochloride (+)-Menthol (-)-Menthol (S)-α-Methyl-4-nitrobenzylamine Hydrochloride (R)-(+)-1-(1-Naphthyl)ethylamine (S)-(-)-1-(1-Naphthyl)ethylamine D-Phenylalaninol L-Phenylalaninol (R)-(+)-1-Phenylethylamine (S)-(-)-1-Phenylethylamine (S)-1-Phenyl-2-(p-tolyl)ethylamine Quinidine Quinidine Sulfate Dihydrate Quinine Quinine Hydrochloride Dihydrate Strychnine Strychnine Hydrochloride Hydrate Strychnine Nitrate Strychnine Sulfate Pentahydrate (R)-(+)-1-(p-Tolyl)ethylamine (S)-(-)-1-(p-Tolyl)ethylamine

Unit Size 25g

5g 25g 5g

25g

5g 25g 25g 100g

1g 1g 5g 5g 25mL 100mL 25mL 100mL 5g 5g 5g 25g

1mL

A1454

A1453 O

O

CH3 C O

A0545 O

C OH

O

CH3 C O

O

C OH HO

for Resolution of Bases

OH O

A0546

B1121

HO

OH O

B1120

C OH

C OH

O

O NH

NH C

NH2

C0012

C0015

CH3

H

CH3 CH3 COOH COOH

C1417

CH3 O

B1143

O

C

CH3 CH2SO3H

CH3 HO3SCH2

CH3 O

D2636 H

O

O H

O

O

H

O

CH3

CH3

CH3 CH2SO2Cl

O

HO

OH O

CH3

O

P OH

CH3 ClSO2CH2

CH3 O

D1911

CH3

O

O

O

C1308

O O

O

P OH

D1386

O

116

O

C0998

O

O

B1144

O

C0972

C1418 H

NH2

O

O

O

25g 25g 200g 25g 25g 25g 250g 25g 25g 25g 500g 500g 500g 1g 5g 5g 25g 25g 500mL 500mL 25g 25g 25g 100g 25g 25g 25g 25g 25g 1mL 5mL

O O

CH3 C O

O

HO

O

OH O

O

CH3 O

O

CH3 C O O

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

O

Optical Resolving Agents

D2645

D1398 D3826

D1354 D3492

O

O

O

CH3 C O

O CH3 C O

Ph

O

HO O

O

O

HO O

O

O

p-Tol

O

HO

O

OH O

p-Tol

O

Ph O 2N

O

G0057

HN

OH . H2O

Ph

O OH

O

O

D1387

D1417 O

Ph OH . H2O

O

O

O

D1853

Synthetic Organic Chemistry

O

G0059

O

NO2

M0021

M0022

O p-Tol

O

O

O

HO

OH O

O OH

O

HO

O OH

NH2

p-Tol

O

O

HO

HO O

NH2

O OH

HO

OH

OH O

OH

O

M0661

M1221

HO

HO

C OH

M0990 CH3

O

O

CH3

C OH

CH3

I0334

I0335 CH3

O

O

O C Cl

O C Cl

CH3

CH3

M1622 CH3

NCO

M1021 CH3

NCO

I0336 O

OH H N O

I0398

P1354

CH3O

CH3

M0824 O

OH O

CH3

NCO

OH H N

CH3

O

P0573

CH3

Q0009

T0026 O

CH3

NCO

HO C OH O

N H

OH

O

O

OH

N H

O

OH

O

HO HO

OH O

OH

OH

OH

T0025

T1702

T1163 NO2

OH

O

HO

OH

H N

OH

OH O

O

OH

NO2

O O2N

NO2 N

OH

O OH

CH3 O

Product No.

Product Name

A1454 A1453 A0545 A0546 B1121 B1120 B1143 B1144 C0012 C0015 C0972 C0998 C1308 C1417

(+)-O-Acetyl-L-mandelic Acid (-)-O-Acetyl-D-mandelic Acid D-Aspartic Acid L-Aspartic Acid (+)-cis-2-Benzamidocyclohexanecarboxylic Acid (-)-cis-2-Benzamidocyclohexanecarboxylic Acid (R)-(-)-1,1'-Binaphthyl-2,2'-diyl Hydrogen Phosphate (S)-(+)-1,1'-Binaphthyl-2,2'-diyl Hydrogen Phosphate (+)-Camphoric Acid (+)-10-Camphorsulfonic Acid (-)-10-Camphorsulfonic Acid (+)-10-Camphorsulfonyl Chloride (-)-10-Camphorsulfonyl Chloride (+)-trans-1,2-Cyclohexanedicarboxylic Anhydride

Unit Size 5g 5g 25g

100mg

1g 100mg 25g 25g 100g 25g 10g 5g 100mg

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

25g 25g 25g 500g 5g 5g 5g 1g 100g 500g 500g 25g 25g 1g

117

Materials Chemistry

M0662

Materials Chemistry

Synthetic Organic Chemistry

Optical Resolving Agents

Product No.

Product Name

C1418 D2636 D1386 D1911 D2645 D1398 D3826 D1354 D3492 D1853 D1417 D1387 G0057 G0059 M0021 M0022 M0662 M0661 M1221 M0990 M1021 I0334 I0335 M1622 M0824 I0336 I0398 P1354 P0573 Q0009 T0026 T0025 T1702 T1163

(-)-trans-1,2-Cyclohexanedicarboxylic Anhydride (+)-Diacetyl-D-tartaric Acid (-)-Diacetyl-L-tartaric Acid (+)-Diacetyl-L-tartaric Anhydride (-)-Diacetyl-D-tartaric Anhydride (+)-Dibenzoyl-D-tartaric Acid Monohydrate (+)-Dibenzoyl-D-tartaric Acid (-)-Dibenzoyl-L-tartaric Acid Monohydrate (-)-Dibenzoyl-L-tartaric Acid (R)-(-)-N-(3,5-Dinitrobenzoyl)-α-phenylglycine (+)-Di-p-toluoyl-D-tartaric Acid (-)-Di-p-toluoyl-L-tartaric Acid D-Glutamic Acid L-Glutamic Acid D-(+)-Malic Acid L-(-)-Malic Acid D-(-)-Mandelic Acid L-(+)-Mandelic Acid (+)-Menthyl Chloroformate (-)-Menthyl Chloroformate (S)-(+)-2-(6-Methoxy-2-naphthyl)propionic Acid (R)-(+)-α-Methylbenzyl Isocyanate (S)-(-)-α-Methylbenzyl Isocyanate (R)-(+)-N-(α-Methylbenzyl)phthalamic Acid (S)-(-)-N-(α-Methylbenzyl)phthalamic Acid (R)-(-)-1-(1-Naphthyl)ethyl Isocyanate (S)-(+)-1-(1-Naphthyl)ethyl Isocyanate D-Pyroglutamic Acid L-Pyroglutamic Acid D-(-)-Quinic Acid D-(-)-Tartaric Acid L-(+)-Tartaric Acid (2R,3R)-Tartranilic Acid (+)-α-(2,4,5,7-Tetranitro-9-fluorenylideneaminoxy)propionic Acid

Unit Size

A1454

100mg

25g 25g

1g

O

CH3 C O

A2128 O

C OH

5g 25g 25g 25g 25g 1g 25g 25g 25g 25g 5g 100g 100g 25g 5mL 5mL 25g 5g 1g 1g 1g 1g 5g 25g 5g 25g 25g 1g

A1453 O

1g 5g 25g 25g 25g 500g 250g 500g 250g 5g 250g 250g 250g 500g 25g 500g 500g 250g 25mL 25mL 500g 25g 5g 5g 1g 5g 5g 25g 500g 25g 500g 500g 5g 1g

O

CH3 C O

O

C OH

for Resolution of Alcohols & Thiols CH2 CH CH2

A1984

B3296

B3549

B1219

N

O S

CH3

N N

S

CH3 COCl O

CH3

118

CH3

C0998

CH3

O

CH3

CH3 O

C1308 CH3 CH2SO2Cl

CH3

CH3 CH3

CH3

CH3 CH3

CH3

CH3

N

CH2 CH CH2

C1022

B1220

CH3 ClSO2CH2

O

O

C1417 CH3

O

O

O

O

C1418 H

O

H

O

O

O H

O

O

H

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

O

CH3

Optical Resolving Agents

M0573

M0571

M1221

CH3

CH3

I0335

CH3

CH3

N0581

CH3

O

O

O C Cl

O C Cl

CH3

CH3

I0336

Synthetic Organic Chemistry

OCH2 C Cl

OCH2 C OH

I0334 CH3

O

O

CH3

M0990 CH3

CH3

CH3

NCO

CH3

I0398

N0582

O

CH3

NCO

CH3

Cl HN

CH3

NCO

O Cl

SO2

HN

SO2

NO2

T2223

SO2

O HN

N

Cl HN

Ph

CH3 N

O

CH3

Si

Materials Chemistry

T1444

NCO

tBu

Ph

SO2

iPr

iPr

iPr

Product No.

Product Name

A1454 A1453 A2128 A1984 B3296 B3549 B1219 B1220 C1022 C0998 C1308 C1417 C1418 M0573 M0571 M1221 M0990 I0334 I0335 N0581 I0336 I0398 N0582 T1444 T2223

(+)-O-Acetyl-L-mandelic Acid 5g 25g (-)-O-Acetyl-D-mandelic Acid 5g 25g (R)-5-Allyl-2-oxabicyclo[3.3.0]oct-8-ene 1g 5g (S)-5-Allyl-2-oxabicyclo[3.3.0]oct-8-ene 1g (+)-Benzotetramisole 200mg 1g 5g (-)-Benzotetramisole 1g 100mg Bis[(2R,3aS,4R,7aS)-octahydro-7,8,8-trimethyl-4,7-methanobenzofuran-2-yl] Ether Bis[(2S,3aR,4S,7aR)-octahydro-7,8,8-trimethyl-4,7-methanobenzofuran-2-yl] Ether 100mg (-)-Camphanic Chloride 1g 5g 25g (+)-10-Camphorsulfonyl Chloride 10g 25g (-)-10-Camphorsulfonyl Chloride 5g 25g 100mg 1g (+)-trans-1,2-Cyclohexanedicarboxylic Anhydride (-)-trans-1,2-Cyclohexanedicarboxylic Anhydride 100mg 1g (-)-Menthoxyacetic Acid 5g 25g (-)-Menthoxyacetyl Chloride 10g (+)-Menthyl Chloroformate 5mL 25mL (-)-Menthyl Chloroformate 5mL 25mL 1g 5g 25g (R)-(+)-α-Methylbenzyl Isocyanate (S)-(-)-α-Methylbenzyl Isocyanate 1g 5g N-(1-Naphthalenesulfonyl)-L-phenylalanyl Chloride 5g (R)-(-)-1-(1-Naphthyl)ethyl Isocyanate 1g 5g (S)-(+)-1-(1-Naphthyl)ethyl Isocyanate 1g 5g N-(4-Nitrophenylsulfonyl)-L-phenylalanyl Chloride 5g N-(p-Toluenesulfonyl)-L-phenylalanyl Chloride 5g Nα-(2,4,6-Triisopropylbenzenesulfonyl)-O-(tert-butyldiphenylsilyl)-π-methyl-L-histidinol 100mg

Unit Size

References 1) S. Hashimoto, S. Kase, A. Suzuki, Y. Yanagiya, S. Ikegami, . 1991, , 833; Tokyo Kasei Kogyo Co., Ltd., Jpn. Kokai Tokkyo Koho 04 273835, 1992. 2) K. Ishihara, Y. Kosugi, M. Akakura, . 2004, , 12212. 3) V. B. Birman, X. Li, . 2006, , 1351. 4) I. Shiina, K. Nakata, . 2007, 48, 8314; I. Shiina, K. Nakata, Y. Onda, . 2008, 5887.

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

119

Materials Chemistry

Synthetic Organic Chemistry

Protection & Derivatization

Protection & Derivatization In organic synthesis, when a reaction is to be carried out selectively at one functional group of a multifunctional compound, other reactive functional groups must be converted into inactive functional groups and protected temporarily. Therefore, appropriate use of protecting agents is very important to the synthetic strategy. Useful protecting agents must have properties as follows: - The protecting agents must selectively react with the desired functional group requiring protection. - The protecting groups must be introduced in high yields without any side reactions. - The protected functional groups should be stable under various reaction conditions. - The protecting groups must be chemoselectively deprotected under specific conditions without deprotection of other kinds of protecting groups. Especially in the synthesis of structurally complex compounds, designing the synthetic strategies such as selection of protecting groups and the efficient deprotection process are key steps to achieve. It is expected that a wide variety of protecting agents are available. The following shows various kinds of protecting agents available for purchase. They are classified from the viewpoint of deprotection conditions. Please make use of this list for your study of organic synthesis.

●Silylation Silyl groups are the most commonly used protecting groups to protect hydroxy groups, and also used for the protection of carboxyl groups and amino groups. TMS and TES groups are commonly used as general protecting groups, while TIPS, TBS (TBDMS) and TBDPS groups are used for introducing bulky substituents. Silyl protecting groups are usually deprotected by acid or fluoride ion mediated hydrolysis. A2298

A2299

A0729

B2334

B1906 tBu

Si

CH3 C

CH3

CH2CH3

CH3 CH3 CH2CH

CH2

CH3CH2 Si

CH2CH

CH2

CH3

CH2CH

CH2

CH2

CH3

CH2CH3

CH3 CH3

Si

CH3

Si CH3

CH3

Si Cl CH3

N

CH3

CH3 C O Si tBu CH3

B1688

B1773

CH3 Cl

Si

CH3 CH2CH2

CH3

Si

CH3 CH3

Cl

CH3 N

CH3

B1436 SiH(CH3)2

CH3 CH3

Si CH2CH2 Si

CH3

B3565

B1699

N CH3

CH3 CH3

H 3C H3C C O Si

CH3

B1043

B0995

SiH(CH3)2

B2697

Cl

CH3

Si Cl CH3 CH3

H3C

T1525

B1223

CH3 CH3 CH3 CH3 C

Si H

CH3 tBu

CH3 CH3

B3566

Si

N

CH3 CH3

O Si C(CH3)3

N

CH3

CH3

CH3

CH3 CH3

C N

B2898

B1663

O

Si O S CF3

H 3C H3C C Si

D2262

Cl

H3C

O

T2116

Br CH3 H3C H3C C Si H H3C

120

H 3C H3C C Si H3C

O O S CF3 O

CH3O Si

C CH3 CH3

CH3 CH3

CH2CH3 CH Si

Cl

CH2CH3

CH3 CH3

CH3 CH3 CH C

Si

CH3 CH3

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

Cl

Protection & Derivatization

T0589

C0306

C2411

CH3

Cl

D1608

D2334

(CH3)2HC Cl

Cl

(CH3)2HC

CH3 CH3

CH3

M0536 OCH3

O

CH3 C N

Si CH3

CH3

T0585

CH3

CH3

CH3

CH3

CH3

CH3

Si CH3

Si Cl

CH3

Si

CH3

O

CH3 CH3

CH3

iPr

O

Si O S CF3 iPr

iPr

O

T1573 CH3

CH3

N O

CH3

iPr

Cl

T1535 Si

C(CH3)3

CH2 C O Si

iPr iPr

S CF3

CH3

N

O

O

O S CF3

T1588

CH2CH3 O

N

O

O

CH3

CH2CH3 O O

C(CH3)3

S O Si

I0324

T1078

T1277

O (CH3)3SiCH2CH2O C O N

CH2CH3

CH3CH2 Si

CH3

T2591

CH

T1689 O CH3 CH3

Si O C CHCH3

CH2CH3

S O Si

O CF3

Materials Chemistry

M1199

D1594 O

CF3

CH3

H3C Cl CH3

Si(CH3)3

CH3

Si O Si Cl CH3

CH(CH3)2

H3C C Si C

Si Cl

T1468 CH3

CH(CH3)2

Si O Si Cl

(CH3)3Si

CH3

CH2CH3

H3C Cl CH3

Si(CH3)3

Si Cl

D3135

Synthetic Organic Chemistry

CH3

CH2CH3 CH3CH2 Si

D2469

N O

Si CH3

CH3

(CH3)3SiO

O

CH3 C CH

C CH3

O

T0871 O CF3

CH3

S O Si CH3 O

CH3

Product No.

Product Name

A2298 A2299 A0729 B2334 B1906 B1688 B1773 B1699 B1436 B0995 B3565 B1043 B2697 T1525 B1223 B3566 B2898 B1663 D2262 T2116 T0589 C0306 C2411 D2469

Allyl(tert-butyl)dimethylsilane Allyltriethylsilane Allyltrimethylsilane Benzylchlorodimethylsilane N,O-Bis(tert-butyldimethylsilyl)acetamide 1,2-Bis(chlorodimethylsilyl)ethane 1,2-Bis[(dimethylamino)dimethylsilyl]ethane 1,2-Bis(dimethylsilyl)benzene tert-Butoxydiphenylchlorosilane (stabilized with CaCO3) tert-Butyldimethylchlorosilane tert-Butyldimethylsilane 1-(tert-Butyldimethylsilyl)imidazole tert-Butyldimethylsilyl N-Phenylbenzimidate tert-Butyldimethylsilyl Trifluoromethanesulfonate tert-Butyldiphenylchlorosilane tert-Butyldiphenylsilane tert-Butyldiphenylsilyl Trifluoromethanesulfonate tert-Butylmethoxyphenylsilyl Bromide Chlorodiethylisopropylsilane Chloro(dimethyl)thexylsilane Chlorotriethylsilane Chlorotrimethylsilane Chlorotris(trimethylsilyl)silane Di-tert-butyldichlorosilane

Unit Size 25mL

5g

5g

5mL 25g 1g

5mL

5g 25mL 1g

1g 5g 5g 25g 25mL 100mL

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

5g 5g 250mL 5g 5g 25g 5g 5mL 25mL 100g 5g 5g 5g 25g 100mL 5g 5g 1g 5g 25g 100g 500mL 5g 5g

121

Materials Chemistry

Synthetic Organic Chemistry

Protection & Derivatization

Product No.

Product Name

D3135 D1608 D2334 T1468 D1594 I0324 M1199 M0536 T1689 T1078 T1588 T2591 T0585 T1277 T1535 T1573 T0871

Di-tert-butylsilyl Bis(trifluoromethanesulfonate) 1,3-Dichloro-1,1,3,3-tetraisopropyldisiloxane 1,3-Dichloro-1,1,3,3-tetramethyldisiloxane Diethylisopropylsilyl Trifluoromethanesulfonate Dimethylisopropylchlorosilane Isopropenyloxytrimethylsilane 1-Methoxy-1-trimethylsilyloxypropene N-Methyl-N-trimethylsilylacetamide Triethylsilyl Trifluoromethanesulfonate Triisopropylsilyl Chloride Triisopropylsilyl Trifluoromethanesulfonate N-[2-(Trimethylsilyl)ethoxycarbonyloxy]succinimide N-Trimethylsilylimidazole N-(Trimethylsilyl)morpholine 3-Trimethylsilyl-2-oxazolidinone 4-Trimethylsilyloxy-3-penten-2-one Trimethylsilyl Trifluoromethanesulfonate

Unit Size 1g 5g 5g 1g 5mL 1g 10g 5g 25mL 5g 1g 25g 5mL

5mL

5g

25g

5g 25g 25g 5g 25mL 5mL 5g 25g 25g 250mL 25g 5g 100g 25mL 5g 25mL 250g

●Acylation Acyl protecting groups are used for the protection of hydroxy groups and amino groups. Acetyl (Ac), benzoyl (Bz), and pivaloyl (Piv) groups are commonly used. Pivaloyl group can selectively protect less sterically-hindered hydroxy groups due to its steric-hindrance. Generally, it is stable under acidic conditions and oxidative conditions. Acyl protecting groups are deprotected under basic conditions or reductive conditions (DIBAL, LAH, etc.). A2301

B0105

B3571 O

O N S

N S

S

M2594

P1894 F F F

122

CF3

F

O

C O

F F

O CF3

C SCH2CH3

S

T0670

F

O

CH3O C O

O

C O S CF3

C

P0677

F

O

T0872 O

O

C Cl

C CH3

F

B3567

O (CH3)3C C Cl

O CF3

N

C N

F

Product No.

Product Name

A2301 B0105 B3571 B3567 T0872 M2594 P1894 P0677 T0670

3-Acetylthiazolidine-2-thione Benzoyl Chloride 3-Benzoylthiazolidine-2-thione Benzoyl Trifluoromethanesulfonate S-Ethyl Trifluorothioacetate Methyl Pentafluorophenyl Carbonate Pentafluorophenyl Trifluoroacetate Pivaloyl Chloride 1-(Trifluoroacetyl)imidazole

Unit Size 5g 25mL 500mL 1g 5g 5g 5mL 1g 5g 25g 25mL 500mL 5g 25g

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

Protection & Derivatization

Acetals and thioacetals are used for the protection of hydroxy groups and thiol groups, the same as for carbonyl groups of aldehydes and ketones. The protecting groups are introduced by the reaction of alcohols or thiols with carbonyl compounds under acidic conditions. Acetals are stable under basic conditions and reductive conditions, and are inert against nucleophiles such as organometallic reagents. The deprotections are carried out by hydrolysis under acidic conditions. Thioacetals are usually stable in both acidic and basic aqueous solutions, and deprotected by hydrolysis with the assist of mercury salts. In addition, it is known that dithiotosylates can be used for converting active methylene compounds into cyclic dithioacetals and the given cyclic dithioacetals are further transformed into carbonyl groups by hydrolysis. Also, the starting methylene groups are given by reductive desulfurization.1,2)

Synthetic Organic Chemistry

A0480

Materials Chemistry

●Acetalization & Thioacetalization

A1247

B2379

B1151

B1257

OCH3

CHO

CH

O

OCH3

H S

CH3 BF4

CH2 C O CH2

S OCH3

OCH3

B3563

B3577

D0555

D0626

D4208 O C H

CH3CH3

(CH3)3SiO

OSi(CH3)3

CH3 C

Si O

CH

CH3CH3

OCH3

OCH3 OCH3

O

O

S

S

CH3

O

CH3

OCH3

E0478

E0479 CH3

CH3 CH3

Si

O(CH2)2O Si CH3

CH3

P1378

E0471

CH3

CH3 CH3

CH3

Si CH3

S(CH2)2S

Si

CH3

CH3

CH3

P0763

Si

S

HS

CH3

O O S S CH2CH2 S S O O

CH3

O O S S(CH2)3S S O O

CH3

I0303

HO

OH

CH2 CH3 C OCH3

D2390

CH3 CH3

E0105

SH

CH3

Product No.

Product Name

A0480 A1247 B2379 B1151 B1257 B3563 B3577 D0555 D0626 D4208 E0478 E0479 E0471 E0105

p-Anisaldehyde p-Anisaldehyde Dimethyl Acetal Benzaldehyde 1,3-Benzodithiolylium Tetrafluoroborate Benzyl Isopropenyl Ether 1,3-Bis(trimethylsilyloxy)propane tert-Butyl[4-(dimethoxymethyl)phenoxy]dimethylsilane 3,4-Dihydro-2H-pyran 2,4-Dimethoxybenzaldehyde 3-(1,3-Dithian-2-ylidene)-2,4-pentanedione Ethylenedioxybis(trimethylsilane) Ethylenedithiobis(trimethylsilane) Ethylene Di(thiotosylate) [Protecting Reagent for Active Methylene] Ethylene Glycol

Unit Size 25mL 500mL 25mL 500mL 500g 5g 1mL 5mL 5g 25g 5g 25mL 100mL 500mL 25g 500g 1g 5g 25g 5g 5g 25g 25g 500g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

123

Synthetic Organic Chemistry

Protection & Derivatization

Product No.

Product Name

I0303 P1378 P0763 D2390

2-Methoxypropene (Phenylthio)trimethylsilane 1,3-Propanedithiol Trimethylene Di(thiotosylate) [Protecting Reagent for Active Methylene]

Unit Size 25mL 500mL 5g 25g 25mL 100mL 5g 25g

●Allyloxycarbonyl, Benzyloxycarbonyl, Benzyl & Allylation

Materials Chemistry

Allyloxycarbonyl (Alloc), benzyloxycarbonyl (Cbz), benzyl (Bn) and allyl groups are commonly used for the protection of amino groups. These protecting groups are generally deprotected by palladium catalysts. B0643

C0274

A1268

A2302

A2303 O

CH2

Br

O

O

CH2

Cl

CH2 CHCH2O C Cl

O

CH2 CHCH2O C O N

CH2 CHCH2O

C O

O

B0411

B0412

C1591

C0176 B3021

CH2Br

CH2Cl

O

B3234

C1124

C1600

CH2O C N

P1281

CH2O C O

O C OCH2

P1277 O

Cl

O

O

CH2O C O N

CH2O C O N

O

O

CF3

Cl3C C OCH2

O2N

C1131 O

NH

O

O

CH2O C Cl

B1483

B3574

M0676

O CH2

M2016

O

O CH2O

CH2

CH2Br Cl3C C OCH2

OCH2

OCH3

OCH3

124

O

NH

O

C O C

O O

N0181

CH2Cl CH2O C OCH2

O

Product No.

Product Name

B0643 C0274 A1268 A2302 A2303 B0411 B0412 C0176 B3021 C1591 B3574 B1483 B3234 C1124

Allyl Bromide Allyl Chloride Allyl Chloroformate N-(Allyloxycarbonyloxy)succinimide Allyl Phenyl Carbonate Benzyl Bromide (stabilized with Propylene Oxide) Benzyl Chloride (stabilized withε-Caprolactam) Benzyl Chloroformate (30-35% in Toluene) Benzyl Chloroformate Benzyl 4-Nitrophenyl Carbonate Benzyl Phenyl Carbonate Benzyl 2,2,2-Trichloroacetimidate Benzyl 2,2,2-Trifluoro-N-phenylacetimidate N-Carbobenzoxyoxysuccinimide

NO2

Unit Size

25g

25g 500g 25mL 500mL 25g 500g 5g 25g 5g 25g 100g 500g 25g 500g 25mL 500mL 25g 250g 5g 5g 25g 25g 1g 5g 25g 250g

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

Protection & Derivatization

Product Name

C1131 P1277 C1600 P1281 M0676 M2016 N0181

N-(2-Chlorobenzyloxycarbonyloxy)succinimide Diallyl Dicarbonate Dibenzyl Carbonate Dibenzyl Dicarbonate 4-Methoxybenzyl Chloride (stabilized with Amylene) 4-Methoxybenzyl 2,2,2-Trichloroacetimidate 4-Nitrobenzyl Bromide

Unit Size 1g 1g 5g

25g

Synthetic Organic Chemistry

Product No.

10g 5g 5g 25g 25mL 5g 500g

●2,2,2-Trichloroethoxycarbonylation 2,2,2-Trichloroethoxycarbonyl (Troc) group is used as a protecting group for hydroxy groups and amino groups. Troc group is generally deprotected by the treatment with zinc powder or by electrolysis. C0795

N

O

Materials Chemistry

T2713

O

O

O C OCH2CCl3

CCl3CH2O C Cl

O

Product No.

Product Name

T2713 C0795

N-(2,2,2-Trichloroethoxycarbonyloxy)succinimide 2,2,2-Trichloroethyl Chloroformate

Unit Size 25g

5g 250g

●Methoxymethylation Methoxymethyl (MOM) group is generally used for the protection of hydroxy groups. They are stable against bases and reducing agents because of their acetal structure. MOM group is deprotected by acid catalyzed hydrolysis. C1339

C0202

C2412

M0680

M0681

CH3 CH3

Si

CH2CH3

CH2CH2OCH2Cl

ClCH2OCH3

Cl

O

CCl3

CH3O(CH2)2OCH2Cl

CH3O(CH2)2OCH2 N CH2CH3 CH2CH3

CH3

Product No.

Product Name

C1339 C0202 C2412 M0680 M0681

2-(Chloromethoxy)ethyltrimethylsilane (stabilized with Diisopropylethylamine) Chloromethyl Methyl Ether Chloromethyl 2,2,2-Trichloroethyl Ether 2-Methoxyethoxymethyl Chloride (2-Methoxyethoxymethyl)triethylammonium Chloride

Cl

Unit Size 25g

5mL 100g

25mL 500g 5g 25mL 500mL 5g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

125

Synthetic Organic Chemistry

Protection & Derivatization



-Butoxycarbonylation

-Butoxycarbonyl (Boc) group is one of the most commonly used protective groups for amino groups in peptide synthesis. It is also used for the protection of hydroxy groups. It is stable under basic hydrolysis conditions and catalytic reduction conditions, and is inert against various nucleophiles. It is deprotected under acidic conditions commonly with trifluoroacetic acid.

B0916

B0988

C1573

CH3 CH3 CH3

O

O C

N N

CH3

O

O

O C O N C

CH3 CH3

CH3

CH3

Materials Chemistry

C0933

B3590 CH3

O Cl

CH3

CH3 CH3

Product Name

B0916 B0988 C1573 B1089 B1969 C0933 B3590 C1574 D3878 D3879 D3880 D1547

N-tert-Butoxycarbonylimidazole 2-(tert-Butoxycarbonyloxyimino)-2-phenylacetonitrile N-(tert-Butoxycarbonyloxy)phthalimide 2-(tert-Butoxycarbonylthio)-4,6-dimethylpyrimidine 1-tert-Butoxycarbonyl-1,2,4-triazole tert-Butyl Carbazate tert-Butyl Phenyl Carbonate tert-Butyl 2,4,5-Trichlorophenyl Carbonate Di-tert-butyl Dicarbonate (ca. 30% in Dioxane) Di-tert-butyl Dicarbonate (ca. 30% in Tetrahydrofuran) Di-tert-butyl Dicarbonate (ca. 30% in Toluene) Di-tert-butyl Dicarbonate

CH3

O C S N

O

O C

N

CH3

CH3

N N

CH3

O

O

CH3

CH3 C O C O C O C CH3 CH3

Product No.

CH3

N

D3878 D3879 D3880 D1547

O C O C CH3 Cl

CH3

O

CH3

O

Cl

CH3

O C O C CH3

CH3

CH3

C1574 O

O

O C NHNH2

B1969

CH3

O

O C O N

CH3

CH3

B1089

CN

CH3

Unit Size 5g 5g 5g 25g 5g 100g 100mL 100g 25g 100g

10g 25g 5g 25g 25g 250g 25g 5g 500g 500mL 500g 500g

●9-Fluorenylmethyloxycarbonylation 9-Fluorenylmethyloxycarbonyl (Fmoc) group is one of the most commonly used protecting groups for amino groups in solid phase peptide synthesis as well as the Boc group. It is readily deprotected by secondary amines such as piperidine while it is stable under acidic conditions. Therefore, when a molecule contains the Fmoc group and the Boc group, only the Boc group can be selectively removed under acidic conditions. F0239

F0197 O O CH2O C O N O

126

F0936 O CH2O C Cl

F

F

F

F

O F

CH2O C O

Product No.

Product Name

F0239 F0197 F0936

N-[(9H-Fluoren-9-ylmethoxy)carbonyloxy]succinimide 9-Fluorenylmethyl Chloroformate 9-Fluorenylmethyl Pentafluorophenyl Carbonate

Unit Size 5g

5g 25g 1g

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

25g 100g 5g

Protection & Derivatization

Trityl (Tr) groups are mainly used for the protection of hydroxy groups. They can selectively protect less sterically-hindered substrates due to their steric-hindrance. They are relatively stable against bases, oxidizing agents, reducing agents and nucleophiles, and the deprotection is carried out under acidic hydrolysis conditions.

B1702

D2504

D1612

CH3O

C Cl

Br

D2915

C Cl

OCH3

T1526

T0512

N

N C

CH3O

C Cl

Cl

C0308

Materials Chemistry

T1071

CH3 CH3

Cl

M0790

O

O

Cl

C O 3

C Br

CBr

N

CBr

C Cl

Cl O

3

Product No.

Product Name

B1702 D2504 D1612 D2915 M0790 T1071 T1526 T0512 C0308

9-Bromo-9-phenylfluorene 2-Chlorotrityl Chloride 4,4'-Dimethoxytrityl Chloride 4-(Dimethylamino)-1-(triphenylmethyl)pyridinium Chloride 4-Methoxytrityl Chloride 4,4',4''-Tris(benzoyloxy)trityl Bromide 4,4',4''-Tris(4,5-dichlorophthalimido)trityl Bromide Trityl Bromide Trityl Chloride

Unit Size 5g 5g 25g 5g

25g

25g 100g

25g 25g 25g 5g 250g 25g 1g 100g 500g

●Others A2555 CH3

C

N N

O

B1655 SO2NCO

SO2Cl SO2Cl

O N

(CH2)3CH3

D0835

CH3

D1463

CH3

C1415 SCl NO2

NO2

S

O P

P Cl

Cl

Cl

NO2

NO2

I0060

M0071

M0802 SO2Cl

O

CH3

O

O

CH3 CH3

F

CH3CH2O C N

CH3

NH Cl3C C O

(CH2)3CH3

D2159

C0683

B1496

SO2Cl

CH3

CH3

D2461

B1128

B1122 B0994

O

O

M1004 SO2Cl

CH3

O C CH2Br

CH3I CH3

Synthetic Organic Chemistry

●Tritylation

OCH3

OCH3

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

127

Protection & Derivatization

Synthetic Organic Chemistry

M0441

N0142 OH

N0507

C1400 SO2F

SO2Cl

O2N

SCH3

P1782

P1614

P1902

O

F

O

O O

F

S O

T1485 NH2

C CH2Br

N H

O

Materials Chemistry

F

F

T0272

T0998

T1606

CH3

T3177

O

CH2CH3

S NCO

O

O

T2872

CH3CH2

CH3

O

T1146

CH2CH3

O

CH3

O C OCH2CH2 Si CH3 CH3

CH3 CH3

T1237

Si

CHN2

CH3

SO2CF3

T1467

NO2

N O O2N

O C OCH2CH2Si(CH3)3

128

S O S O

N

BF4

T2544

N N

O

O CH3

N

CH3

T2590

N

O

SO2Cl

N

NO2

O C Cl

NO2

P2188

CF3

SCl

O

NO2

F

N0363

N

N

O C S Cl

Cl3CO

C OCH2CH2Si(CH3)3

OCCl3

O

Product No.

Product Name

A2555 B1122 B0994 B1128 B1655 B1496 D2461 D2159 D0835 D1463 C1415 C0683 I0060 M0071 M0802 M1004 M0441 N0142 N0507 C1400 N0363 P2188 P1782 P1614 P1902 T1485 T0272 T0998 T1606 T3177 T1146 T2590

5-Acetyl-1,3-dimethylbarbituric Acid Bansyl Chloride (10% in Hexane) Bansyl Chloride 1,2-Benzenedisulfonyl Dichloride Benzenesulfonyl Isocyanate tert-Butyl 2,2,2-Trichloroacetimidate Dibenzosuberyl Chloride Dimethylthiophosphinoyl Chloride 2,4-Dinitrofluorobenzene 2,4-Dinitrophenylsulfenyl Chloride Diphenylphosphinic Chloride N-Ethoxycarbonylphthalimide Iodomethane (stabilized with Copper chip) 2-Mesitylenesulfonyl Chloride 4-Methoxybenzenesulfonyl Chloride 4'-Methoxyphenacyl Bromide 4-(Methylthio)phenol 2-Nitrobenzenesulfonyl Chloride 4-Nitrobenzenesulfonyl Fluoride 4-Nitrophenyl Chloroformate 2-Nitrophenylsulfenyl Chloride Pentafluorophenyl Trifluoromethanesulfonate Phenacyl Bromide Phthalic Anhydride 2-(1H-Pyrazol-5-yl)aniline p-Toluenesulfonic Anhydride p-Toluenesulfonyl Chloride p-Toluenesulfonyl Isocyanate Triethyloxonium Tetrafluoroborate (15% in Dichloromethane, ca. 1mol/L) [Ethylating Reagent] 1-(Trifluoromethanesulfonyl)imidazole Trimethylsilyldiazomethane (ca. 10% in Hexane, ca. 0.6mol/L) 1-[2-(Trimethylsilyl)ethoxycarbonyloxy]benzotriazole

Unit Size

1g

10mL 25g

25g

10mL

5g 5mL 5g 25g 5g 5mL 25mL 5g 25g 1g 5g 25g 500g 5g 10g 25g 25g 500g 100mL 300mL 25g 500g 100g 500g 5g 25g 25g 250g 100g 500g Price on request 25g 250g 25g 100g 200mg 1g 25g 500g 500g 1g 5g 25g 25g 500g 25g 500g 100mL 1g 5g 25mL 100mL 1g 5g 1mL 1g 5g

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

Protection & Derivatization

Product Name

T2872 T2544 T1237 T1467

4-[2-(Trimethylsilyl)ethoxycarbonyloxy]nitrobenzene 2-(Trimethylsilyl)ethyl 3-Nitro-1H-1,2,4-triazole-1-carboxylate Triphenylmethanesulfenyl Chloride Triphosgene

Unit Size 1g 25g

Synthetic Organic Chemistry

Product No.

5g 5g 10g 250g

References 1) R. B. Woodward, I. J. Pachter, M. L. Scheinbaum, . 1971, , 1137. 2) R. J. Bryant, E. McDonald, . 1975, 3841. 3) Review: . 3rd ed., ed. by T. W. Greene, P. G. M. Wuts, John Wiley & Sons, Inc., New York, 1999.

Materials Chemistry

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

129

Synthetic Organic Chemistry

Ionic Liquids

Ionic Liquids Ionic liquids are organic salts in the liquid state at room temperature and have gained much attention as green reaction solvents taking the place of organic solvents in organic synthesis because of their properties such as almost no vapor pressure and non-flammability. Typical cations are imidazolium, pyridinium, quaternary ammonium and quaternary phosphonium. On the other hand, typical anions are halide, triflate, tetrafluoroborate and hexafluorophosphate. Cationic Parts

N

R

Anionic Parts

R

Cl Br

Materials Chemistry

R N R N

N

R

R

CH3COO CF3COO

R R

TfO

R P R N R

R

N

R

R

Water Solubility

I

Tf2N

R

BF4 PF6

BR4

The characteristic feature of ionic liquids is high flexibility for their own molecular design. Their physical properties of melting points, viscosity and electric conductivity can be controlled by the combination of both cationic and anionic ions. In addition, by introducing functional moieties into ionic liquids, they are expected to be used for not only organic solvents but also a wide range of usages such as organocatalysts, metal-scavengers, electrolytes and lubricants.

N

CH3 N

CH3

N

N

B2195

PF6

CH3

Lipase

B3028

(CH2)3CH3

C4H9

CH3(CH2)15O(CH2CH2O)nSO3

Solvent

Enzymatic Catalyst

Recently, SILC (Supported Ionic Liquid Catalyst), wherein catalysts consisting of some metals such as palladium and ruthenium supported on silica gel or alumina gel with the use of ionic liquids, has attracted attention. Generally, ionic liquids have higher viscosity compared to organic solvents, and this property often makes the isolation of reaction products difficult. In contrast, SILC is solid state and can be easily removed from the reaction products by filtration. Furthermore, the collected SILC after the reactions is usable repeatedly. D3341

D3240 N

Imidazolium Salts

CH3

N

Cl

N

E0490 CH3 CH3O

N

CH3

CH3O

CH3

mp 125 ℃ E0556

E0543 N

CH3

N

N Br

CH2CH3

N

N I

N

CH2CH3

mp 84 ℃

CH3

N

N

CF3SO3

CH3

N

CF3BF3

CH2CH3

CH2CH3

Liquid

Cl

N

E0836 N

CH3SO3

CH3

Liquid

CH3

CH2CH3

mp 79 ℃

P O

E0494

CH3

CH2CH3

mp 74 ℃

130

E0755

N

O

Liquid

Liquid

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Ionic Liquids

E0650

E0754

CH3

N

HSO4

N CH2CH3

CH3CH2OSO3

N

N

(CF3SO2)2N

FeCl4

I

N

Liquid

N (CH2)3CH3

(CF3SO2)2N

Liquid

Liquid H1099

N

N

Br

N

N

N Cl

N

(CH2)7CH3

N N

Liquid B2473 N N

CH2CH2CH3

Liquid

N

CH3

N

CH2CH2CH3

Solid

CH3 CH3

N

CF3SO3 N

(CH2)3CH3

fp 34 ℃

I CH3

N

B2474 N

BF4 CH3

CH3

Liquid

CH3

(CH2)3CH3

mp 99 ℃

N (CF3SO2)2N

CH3 PF6 CH3

(CH2)3CH3

mp 44 ℃

mp 38 ℃

H1286 CH3

N

(CF3SO2)2N N

N

(CH2)3CH3

B3159 N

N

CH3

CH3

B4182

Cl

Liquid D3903

Liquid

CH3

(CF3SO2)2N

Br

N

(CH2)7CH3

CH2CH3

B2475

CH3 CH3

(CF3SO2)2N

CH3

Liquid

N

(CH2)9CH3

Liquid D4289

N

CH3

N

(CH2)7CH3

N

PF6

E0753

N

PF6

CH3

Liquid

CH3

Liquid

(CH2)5CH3

D4351

CH3

N

N

(CF3SO2)2N

Liquid M2063

Cl

N

(CH2)5CH3

M1904

CH3

N

CH3

Liquid

(CH2)5CH3

Liquid M2062

N

H1098

N

(CH2)5CH3

(CH2)5CH3

N SCN

Liquid

CH3 BF4

CH3

(CH2)3CH3

H1423

CH3

N

FeCl4

N

Liquid H1097

N

(CH2)3CH3

(CH2)3CH3

H1227

Liquid

CH3

N

BF4

N (CH2)3CH3

B4091

CH3

N

CF3BF3

N

CH3

N

Liquid B2672

N

CH3

(CH2)3CH3

mp 8 ℃

CH3 PF6

CF3SO3

mp 77 ℃ B2195

N

(CH2)3CH3

B2477 N

mp 41 ℃

CH3

N

(CH2)3CH3

Br

N (CH2)3CH3

B3542 N

Br3

N

(CH2)3CH3

B2320

Liquid

CH3

N

Cl

N

CH3

N

(CH2)3CH3

B2337

CH3

N

CH3

CH3

N

(CH2)3CH3

CH3 CH3

I

(CH2)5CH3

Liquid

Solid

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

131

Materials Chemistry

B3596

B2708

N

CH2CH2CH3

Liquid

mp 61 ℃ B2193

I

N

CH2CH3

Liquid

CH2CH3

Liquid

CH3

N

PF6

N

B2194

CH3

N

CH2CH3

BF4

Liquid M1440

CH3

N

CH2CH3

Liquid

CH3

CH3

N

CH2CH3

E0706

N

N

(NC)2N

N

CH2CH3

E0599

E0493

CH3

N

Liquid

N

E0496

Synthetic Organic Chemistry

CH3

N

E0680

Materials Chemistry

Synthetic Organic Chemistry

Ionic Liquids

Product No.

Product Name

D3341 D3240 E0490 E0543 E0556 E0755 E0494 E0836 E0754 E0650 E0680 E0496 E0493 E0599 E0706 M1440 B2194 B2193 B2708 B3596 B2337 B3542 B2195 B2320 B2477 B2672 B4091 H1097 H1227 H1099 H1423 H1098 M1904 M2062 M2063 D4351 E0753 D3903 D4289 B2473 B2475 B4182 B2474 B3159 H1286

1,3-Dimethylimidazolium Chloride 1,3-Dimethylimidazolium Dimethyl Phosphate 1-Ethyl-3-methylimidazolium Chloride 1-Ethyl-3-methylimidazolium Bromide 1-Ethyl-3-methylimidazolium Iodide 1-Ethyl-3-methylimidazolium Methanesulfonate 1-Ethyl-3-methylimidazolium Trifluoromethanesulfonate 1-Ethyl-3-methylimidazolium Trifluoro(trifluoromethyl)borate 1-Ethyl-3-methylimidazolium Hydrogen Sulfate 1-Ethyl-3-methylimidazolium Ethyl Sulfate 1-Ethyl-3-methylimidazolium Dicyanamide 1-Ethyl-3-methylimidazolium Tetrafluoroborate 1-Ethyl-3-methylimidazolium Hexafluorophosphate 1-Ethyl-3-methylimidazolium Bis(trifluoromethanesulfonyl)imide 1-Ethyl-3-methylimidazolium Tetrachloroferrate 1-Methyl-3-propylimidazolium Iodide 1-Butyl-3-methylimidazolium Chloride 1-Butyl-3-methylimidazolium Bromide 1-Butyl-3-methylimidazolium Iodide 1-Butyl-3-methylimidazolium Tribromide 1-Butyl-3-methylimidazolium Trifluoromethanesulfonate 1-Butyl-3-methylimidazolium Trifluoro(trifluoromethyl)borate 1-Butyl-3-methylimidazolium Tetrafluoroborate 1-Butyl-3-methylimidazolium Hexafluorophosphate 1-Butyl-3-methylimidazolium Bis(trifluoromethanesulfonyl)imide 1-Butyl-3-methylimidazolium Tetrachloroferrate 1-Butyl-3-methylimidazolium Thiocyanate 1-Hexyl-3-methylimidazolium Chloride 1-Hexyl-3-methylimidazolium Bromide 1-Hexyl-3-methylimidazolium Tetrafluoroborate 1-Hexyl-3-methylimidazolium Bis(trifluoromethanesulfonyl)imide 1-Hexyl-3-methylimidazolium Hexafluorophosphate 1-Methyl-3-n-octylimidazolium Bromide 1-Methyl-3-n-octylimidazolium Chloride 1-Methyl-3-n-octylimidazolium Hexafluorophosphate 1-Decyl-3-methylimidazolium Bis(trifluoromethanesulfonyl)imide 1-Ethyl-2,3-dimethylimidazolium Bis(trifluoromethanesulfonyl)imide 1,2-Dimethyl-3-propylimidazolium Iodide 2,3-Dimethyl-1-propylimidazolium Bis(trifluoromethanesulfonyl)imide 1-Butyl-2,3-dimethylimidazolium Chloride 1-Butyl-2,3-dimethylimidazolium Tetrafluoroborate 1-Butyl-2,3-dimethylimidazolium Trifluoromethanesulfonate 1-Butyl-2,3-dimethylimidazolium Hexafluorophosphate 1-Butyl-2,3-dimethylimidazolium Bis(trifluoromethanesulfonyl)imide 1-Hexyl-2,3-dimethylimidazolium Iodide

Unit Size

Pyridinium Salts

5g

N

Cl

5g 5g 5g 5g 5g 5g 5g 5g 5g 5g 5g 5g 5g 5g 5g 5g 5g 5g 5g 5g 5g 5g 5g 5g

B1329

Br

N

CH2CH3

Solid B3232

B1743

B2196

5g 25g

5g

N

CH2CH3

25g 25g 250g 25g 25g 25g 25g 5g 25g 25g 5g 25g 25g 25g 5g 25g 100g 5g 25g 5g 25g 5g 25g 25g 25g 25g 25g 25g 25g 25g 25g 25g 25g 25g 25g 25g 25g 25g 25g 25g 25g 25g 25g 25g 5g

5g 5g 1g 5g 5g 5g

E0171

E0544

5g 5g 25g 5g 5g 5g 5g

Cl

(CH2)3CH3

mp 120 ℃ P1393

mp 132 ℃ B3425 CH3

N

Br

(CH2)3CH3

mp 104 ℃

132

N

BF4

(CH2)3CH3

N

PF6

(CH2)3CH3

Liquid

N

Cl

N

CH2CH2CH3

mp 75 ℃

Cl

(CH2)3CH3

Solid

Solid

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Ionic Liquids

E0681

B3104

B3426

Br

N

CH3CH2OSO3

N

CH2CH3

(CH2)3CH3

CH3

CH2OH

CH3CH2OSO3

CH3 Br

Cl N

CH2CH3

Solid

B2700

N

(CH2)3CH3

Liquid

Liquid

(CH2)3CH3

mp 160 ℃

mp 137 ℃

B2701 CH3 PF6

Synthetic Organic Chemistry

CH3

CH3 N

E0682

N (CH2)3CH3

mp 42 ℃

Product Name

E0544 E0171 B1329 B1743 B3232 B2196 P1393 B3425 B3104 E0681 E0682 B3426 B2700 B2701

1-Ethylpyridinium Chloride 1-Ethylpyridinium Bromide 1-Butylpyridinium Chloride 1-Butylpyridinium Bromide 1-Butylpyridinium Tetrafluoroborate 1-Butylpyridinium Hexafluorophosphate 1-Propylpyridinium Chloride 1-Butyl-3-methylpyridinium Chloride 1-Butyl-3-methylpyridinium Bromide 1-Ethyl-3-methylpyridinium Ethyl Sulfate 1-Ethyl-3-(hydroxymethyl)pyridinium Ethyl Sulfate 1-Butyl-4-methylpyridinium Chloride 1-Butyl-4-methylpyridinium Bromide 1-Butyl-4-methylpyridinium Hexafluorophosphate

Materials Chemistry

Product No.

Unit Size 5g

25g 25g 25g 25g 25g 25g 5g 5g 25g 25g 5g 25g 25g 25g

10g 5g 5g 5g 1g 5g 5g 5g 5g 5g

B3424

Br

Piperidinium Salts CH3

N

(CH2)3CH3

Solid

Product No.

Product Name

B3424

1-Butyl-1-methylpiperidinium Bromide

Unit Size 5g

T2761

A2274

CH3

T2679

N CH2CH2CH3

CH3(CH2)4 N CH2CH3

CH3(CH2)3 N

(CH2)3CH3 Cl

(CH2)3CH3

mp 70 ℃

M1660

(CH2)3CH3 CH3(CH2)3 N

(CH2)3CH3 Br

(CH2)3CH3

mp 103 ℃

(CF3SO2)2N

Liquid C1966

(CH2)7CH3 CH3 N

N CH3

(CH2)7CH3

CH3

(CF3SO2)2N

(CF3SO2)2N

Liquid

Liquid T1124

CH3

(CH2)7CH3

(CH2)3CH3

(CH2)3CH3

(CF3SO2)2N

Liquid

(CH2)3CH3

CH3 N

CH2CH3

CH3 (CF3SO2)2N

T0054

T0055

(CH2)3CH3

CH2CH3

CH3

Ammonium, Phosphonium, Sulfonium Salts

25g

(CH2)3CH3 CH3(CH2)3 P

(CH2)3CH3 Br

(CH2)3CH3

Solid

mp 104 ℃

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

133

Ionic Liquids

Synthetic Organic Chemistry

T2680

T2564

H1047

(CH2)3CH3 CH3

P

(CH2)3CH3

(CH2)3CH3

CH3OCH2CH2 P

(CH2)3CH3

(CH2)3CH3

(CH2)3CH3

Liquid

Materials Chemistry

(CH2)3CH3 CH3(CH2)3 P

Liquid

CH2CH3

(CH2)15CH3 Br

CH3CH2

(CH2)3CH3

(CF3SO2)2N

(CF3SO2)2N

T2314

S

(CF3SO2)2N

CH2CH3

mp 61 ℃

Liquid

Product No.

Product Name

T2761 A2274 T2679 T0055 T0054 M1660 C1966 T1124 T2680 T2564 H1047 T2314

Trimethylpropylammonium Bis(trifluoromethanesulfonyl)imide Amyltriethylammonium Bis(trifluoromethanesulfonyl)imide Tributylmethylammonium Bis(trifluoromethanesulfonyl)imide Tetrabutylammonium Chloride Tetrabutylammonium Bromide Methyltri-n-octylammonium Bis(trifluoromethanesulfonyl)imide Cyclohexyltrimethylammonium Bis(trifluoromethanesulfonyl)imide Tetrabutylphosphonium Bromide Tributylmethylphosphonium Bis(trifluoromethanesulfonyl)imide Tributyl(2-methoxyethyl)phosphonium Bis(trifluoromethanesulfonyl)imide Tributylhexadecylphosphonium Bromide Triethylsulfonium Bis(trifluoromethanesulfonyl)imide

Unit Size

M2098

E0977

Pyrrolidinium Salts

CH3

5g

N

25g

100g

B3358

CH3

N

Cl CH3

CH2CH2CH3

Solid

N

(CH2)3CH3

Liquid

Solid

B2851

B3427

(CF3SO2)2N

Br CH3

5g 25g 100g

(CF3SO2)2N

BF4 CH2CH3

5g 25g

25g 5g 25g 100g 500g 5g 5g 500g 5g 5g 25g 5g

N

(CH2)3CH3

CH3

N

(CH2)3CH3

Solid

Liquid

Product No.

Product Name

E0977 M2098 B3358 B3427 B2851

1-Ethyl-1-methylpyrrolidinium Tetrafluoroborate 1-Methyl-1-propylpyrrolidinium Bis(trifluoromethanesulfonyl)imide 1-Butyl-1-methylpyrrolidinium Chloride 1-Butyl-1-methylpyrrolidinium Bromide 1-Butyl-1-methylpyrrolidinium Bis(trifluoromethanesulfonyl)imide

Unit Size 5g 5g 5g 5g 5g

25g 25g 25g 25g 25g

References 1) F. Kerton, R. Marriott, in 2) P. Wasserscheid, T. Welton, in

134

, RSC Publishing, 2009. , Wiley-VCH, Weinheimm, 2003.

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Fluorous Solvents

Solvents containing fluorine with a relatively large component in molecules are called fluorous solvents. Most fluorous solvents have high thermostability and chemostability and are low in toxicity. (CF2)nCF3 P1384 (n=1), b.p. 135 °C CF3(CF2)nCF3 P0839 (n=4), b.p. 60 °C CF3(CF2)n P0851 (n=5), b.p. 82 °C N P1051 (n=4) O0268 (n=6), b.p. 104 °C (CF2)nCF3 E0485 (n=7), b.p. 125 °C

F F

F F F

H0085 b.p. 81 °C

F CF3

CF3

F

F

F

F

F F

F

F

F F

F

F

F

F

F

F

F

F

F

F

F F

F

F

P0846 b.p. 76 °C

F F F

P0856 b.p. 104 °C

F

F F

F

F

P0837 b.p. 142 °C

The characteristic feature of fluorous solvents is that they mix with neither common organic solvents nor water at room temperature thus forming biphasic systems, and they dissolve fluorine-rich compounds well. To utilize these features, a method of separation and purification called a fluorous biphase system (FBS) has been developed. In this synthetic manner, after the reaction of substrates having a perfluoroalkyl group with some reactants in a mixture of fluorous/organic solvents, the fluorous compounds can be selectively recovered from phase-separated fluorous layer. On the other hand, organic compounds without fluorine containing functional groups are recovered from the phase-separated organic layer, so that the FBS allows some purification processes such as column chromatography to be omitted. For example, Curran . applied FBS to the Stille coupling reaction of organotin compounds having a fluoroalkyl group with aryl bromides. Generally, organotin byproducts are hard to remove but fluorinated organotin byproducts in FBS are easily dissolved in the phase-separated fluorous layer, and can be simply removed by extraction. Water Phase

(C6F13CH2CH2)3SnPh PdCl2(PPh3)2 LiCl +

Br

O2N

D2669

DMF/THF

E0485

P1420

P0851 F

F

F

CF3 F

85% Fluorous Phase

(C6F13CH2CH2)3SnCl 99%

CF3(CF2)3

(CF2)3CF3 N (CF2)3CF3

H0085

F

P1755

CF3(CF2)7Br

CF3(CF2)10CF3

P0837 F

F F

F

O2N

H0946

CF3

F F

CH2Cl2 Phase

CH2Cl2 CF3(CF2)4CF3 H2O

P0074

CF3(CF2)7CF3

CF3CHFCHFCF2CF3

FBS

Inorganic salt and water soluble waste

F

F

CF3(CF2)5CF3 F

F F

F

O0268 F

F F F

F

F

F

F

F

F F

F

F F F

F

CF3(CF2)6CF3

F

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

135

Materials Chemistry

F

F

Synthetic Organic Chemistry

Fluorous Solvents

Fluorous Solvents

Synthetic Organic Chemistry

O0292

P0856 F

F

F

F

F

F F

F

F

CF3 F

P1051

P0839

CF3 F

F

F

F

CF2CF3 CF3CF2

N

CF2CF3

C5F11 C5F11 N C5F11

CF3(CF2)4CF3

F

P0846

T1012 F

F

F

F

F F

Materials Chemistry

P1348

F

F

CF3CF2CF2CF

CF3 CF3

F

Product No.

Product Name

D2669 E0485 P0074 H0946 P1755 P1420 P0851 H0085 P0837 O0268 O0292 P0856 P1348 P0867 P1051 P0839 P0846 T1012

2H,3H-Decafluoropentane Eicosafluorononane Heptacosafluorotributylamine [for Mass spectrometry] Heptadecafluoro-n-octyl Bromide Hexacosafluorododecane Hexadecafluoro(1,3-dimethylcyclohexane) Hexadecafluoroheptane (mixture of isomers) Hexafluorobenzene Octadecafluorodecahydronaphthalene Octadecafluorooctane Octafluorocyclopentene Octafluorotoluene Pentadecafluorotriethylamine Perfluoro(2-butyltetrahydrofuran) (so called) Perfluorotriamylamine (so called) Tetradecafluorohexane Tetradecafluoromethylcyclohexane Tetradecafluoro-2-methylpentane

Unit Size 25g 25g 5g

10g 25g

5g 5g

10g

25g 25g

500g 10g 100g 25g 1g 25g 25g 250g 25g 10g 50g 25g 25g 25g 25g 250g 100g 25mL

References 1) F. Kerton, R. Marriott, in 2) M. Hoshino, P. Degenkolb, D. P. Curran,

136

. 1997,

, RSC Publishing, 2009. , 8341.

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Polymer-supported Reagents

The utility of polymer-supported reagents was discovered by Merrifield and recently, over 300 recyclable polymer-supported reagents have been reported. The ideal polymer-supported reagents need to satisfy the conditions that their reactivity is comparable to the related liquid-phase reactions, and they are separable, recoverable and recyclable after the reactions. By utilizing the above mentioned characteristics, the polymer-supported reagents are used in the synthetic means shown below. 1) 2) 3) 4)

Resins for solid-phase reactions Scavengers for excess agents Easily reusable polymer-supported organic and organometallic catalysts Immobilization of barely-separable/harmful reagents

H2

Pd / (PSi-Al2O3) [P1944]

neat, rt, 0.2 mL min-1

14.5 g 1.5 h TON 2200

On the other hand, Ikegami . have developed an amphiphilic polymer-supported palladium catalyst with affinity for water and organic solvents and applied it for organic synthesis. Palladium-supported poly ( -isopropylacrylamide) (PNIPAAm) (P1425), polymer-supported tungsten (P1697) and polymer-supported ruthenium (P1698) show amphiphilicity and incorporate both hydrophilic/hydrophobic substrates and reagents to make the reactions proceed smoothly. These catalysts are applicable to Suzuki-Miyaura coupling reactions, oxidative cyclizations of ω-unsaturated alcohols and carboxylic acids in the presence of hydrogen peroxide, and oxidations by molecular oxygen. After completion of these reactions, they can be recycled and reused. I +

B(OH)2 recycle average yield 95% in 10 times

HN

Ph P Ph

O 20

PdCl2 2

[P1425]

recovery

n

5.0 x 10-5 mol eq.

A2006

B2372

B2370

B2371

B2292 F

F

F

F

CH2NHCH2CH2NH P

P

CH2O

C NH(CH2)4NHO2S O2N

P

CH2O

C NH(CH2)2NHO2S O2 N

P

CH2O

C NH(CH2)3NHO2S

CH

P

O2 N

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

SO2CF3 SO2CF3

137

Materials Chemistry

Also, the polymer-supported reagents are used in continuous plug flow reactors. Kobayashi . have developed a polysilane-supported palladium catalyst (Pd/(PS-Al2O3)) and introduced it into the continuous plug flow reactors to perform hydrogenations under hydrogen gas flow conditions, Suzuki-Miyaura coupling reactions, Sonogashira coupling reactions and hydrosilylations.

Synthetic Organic Chemistry

Polymer-supported Reagents

Polymer-supported Reagents

Synthetic Organic Chemistry

C2141

D3525

M1452

M1857 O

CH3

CH2N C N P

P

P1415

CH2 N (CH2)3N C NCH2CH3 CH3

O C CH3

O O PEG O C (CH2)2 C O

O C CH3

P

P

P1425

CH2

O

Materials Chemistry

N

CH CH3 CH3

CH3 NH

O

P 20

2

C O

C O

NH

NH

CH CH3

PdCl2

CH2 N

O

P

P1698

CH3

(CH2 CH)x (CH2 CH)y (CH2 CH)z C O C O C O

(CH2)3

CH3 N CH3 C12H25 n

n

PW12O403

P1719

CH3

(CH2 CH)12 (CH2 CH)1

O

P1944

N

P1697

CH3

Cl Ru Cl P

I

CH2

P

Cl

P1427 O

P

D2766

NH

NH

CH CH3

N

(CH2)3

CH3 CH3 N CH3

n

C12H25 RuO4 n

n/3

S0545 CH3

Pd / (PSi-Al2O3)

P

SO2Cl

CH2 N CH3 CH3

P

BH3CN

Product No.

Product Name

A2006

N-(2-Aminoethyl)aminomethyl Polystyrene Resin cross-linked with 1% DVB (50-100mesh)

B2372

N-(4-Benzyloxytrityl)-N '-(2-nitrobenzenesulfonyl)-1,4-diaminobutane Resin

B2370

N-(4-Benzyloxytrityl)-N '-(2-nitrobenzenesulfonyl)-1,2-diaminoethane Resin

B2371

N-(4-Benzyloxytrityl)-N '-(2-nitrobenzenesulfonyl)-1,3-diaminopropane Resin

B2292

Bis(trifluoromethanesulfonyl)methyltetrafluorophenyl Polystyrene Resin

C2141 D3525 D2766 M1452 M1857 P1415 P1427 P1425 P1697 P1698 P1944 P1719 S0545

(3.1-3.5mmol/g)

Unit Size 5g

25g 1g

cross-linked with 1% DVB (200-400mesh) (0.9-1.1mmol/g)

1g

cross-linked with 1% DVB (200-400mesh) (0.9-1.1mmol/g)

1g

cross-linked with 1% DVB (200-400mesh) (0.9-1.1mmol/g)

100mg N-Cyclohexylcarbodiimidomethyl Polystyrene Resin cross-linked with 1% DVB (50-100mesh) (1.4-1.6mmol/g) 5g 1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide Resin cross-linked with 1% DVB (50-100mesh) (1.0-1.3mmol/g) 5g 4-Diphenylphosphinomethyl Polystyrene Resin cross-linked with 2% DVB (200-400mesh) (0.5-1.0mmol/g) 5g 3-Methyl-2-oxoimidazolidin-1-ylmethyl Polystyrene Resin cross-linked with 1% DVB 1g 5g Morpholinomethyl Polystyrene Resin cross-linked with 1% DVB (50-100mesh) (2.9-3.5mmol/g) Poly[4-(diacetoxyiodo)styrene] 1g 5g Polyethylene Glycol-bound Ruthenium Carbene Complex 100mg Poly[N-isopropylacrylamide-co-4-(diphenylphosphino)styrene] Palladium(II) Dichloride 100mg (ratio, acrylamide:phosphine=20:2) Poly[[N-isopropylacrylamide-co-[N-[3-(dodecyldimethylammonio)propyl]acrylamide]]phosphotungstate] 200mg 1g Poly[[N-isopropylacrylamide-co-[N-[3-(dodecyldimethylammonio)propyl]acrylamide]co-(1,3,5-triacryloylhexahydro-1,3,5-triazine)]perruthenate] 200mg 1g Poly(methylphenyl)silane supported Palladium/Alumina Hybrid Catalyst [=Pd / (PSi-Al2O3)] 1g (Polystyrylmethyl)trimethylammonium Cyanoborohydride 5g 25g cross-linked with 10% DVB (30-50mesh) (2.6-3.0mmol/g) Sulfonyl Chloride Polystyrene Resin cross-linked with 1% DVB (50-100mesh) (4.5-5.3mmol/g) 5g 25g cross-linked with 2% DVB (200-400mesh) (0.9-1.2mmol/g)

References 2013, 1) J.-W. Lee, T. Mayer-Gall, K. Opwis, C. E. Song, J. S. Gutmann, B. List, , 1225. 2) H. Oyamada, R. Akiyama, H. Hagio, T. Naito, S. Kobayashi, . 2006, 4297. 3) a) Y. M. A. Yamada, K. Takeda, H. Takahashi, S. Ikegami, . 2003, , 7733. b) Y. M. A. Yamada, K. Takeda, H. Takahashi, S. Ikegami, . 2002, , 3371. 2004, c) Y. M. A. Yamada, H. Tabata, M. Ichinohe, H. Takahashi, S. Ikegami, , 4087. d) H. Hamamoto, Y. Suzuki, Y. M. A. Yamada, H. Tabata, H. Takahashi, S. Ikegami, 4536.

138

. 2005,

,

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Boronic Acids & Boronic Acid Derivatives

B0529

C2188

Synthetic Organic Chemistry

Boronic Acids & Boronic Acid Derivatives

C2893 B(OH)2

Alkyl & Alkenylboronic Acids

CH3

B(OH)2 B(OH)2

E0913

F0280

F0664

H0913

B(OH)2

B(OH)2

Fe

CH3CH2B(OH)2

Fe

I0597

I0787

B(OH)2 CH3

P1942

M1553

CH3 CH3

B(OH)2

CHB(OH)2

O0452

CH3B(OH)2

CH3

P2267

B(OH)2

CH3

B(OH)2

T2498 CH2 CH

CH3

CH3 B(OH)2

B(OH)2

CH3

Materials Chemistry

C2442

B(OH)2

B O

O B

B

CH CH2

O

CH CH2

N

Product No.

Product Name

B0529 C2188 C2893 C2442 E0913 F0280 F0664 H0913 I0597 I0787 M1553 O0452 P2267 P1942 T2498

Butylboronic Acid (contains varying amounts of Anhydride) Cyclohexylboronic Acid (contains varying amounts of Anhydride) 1-Cyclopentenylboronic Acid (contains varying amounts of Anhydride) Cyclopentylboronic Acid (contains varying amounts of Anhydride) Ethylboronic Acid (contains varying amounts of Anhydride) Ferroceneboronic Acid (contains varying amounts of Anhydride) 1,1'-Ferrocenediboronic Acid (contains varying amounts of Anhydride) Hexylboronic Acid (contains varying amounts of Anhydride) Isobutylboronic Acid (contains varying amounts of Anhydride) Isopropylboronic Acid (contains varying amounts of Anhydride) Methylboronic Acid (contains varying amounts of Anhydride) n-Octylboronic Acid (contains varying amounts of Anhydride) Pentylboronic Acid (contains varying amounts of Anhydride) Propylboronic Acid (contains varying amounts of Anhydride) 2,4,6-Trivinylboroxin - Pyridine Complex

Unit Size 1g

1g

5g 1g 1g 1g 1g 100mg 1g 5g 5g 1g 1g 5g 5g 1g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

25g 5g 5g 5g 5g 1g 1g 5g 25g 25g 5g 5g 25g 25g 5g

139

Boronic Acids & Boronic Acid Derivatives

Synthetic Organic Chemistry

A2453

A1942 B(OH)2 B(OH)2

B(OH)2

Arylboronic Acids

O

O NH C CH3

C CH3

O C CH3 O

A1907

A2745

A1281

B(OH)2

B(OH)2

A1774 B(OH)2

A1843

A2328

B3683

B(OH)2

B(OH)2

C OCH2

B4590

F

B2145

B2488

B(OH)2

B(OH)2

B(OH)2

OCH2

CH2O

F

B(OH)2

OCH2

B2489

B2294

B2490

B3927

B(OH)2

B1886

B2860

(HO)2B

B(OH)2

B3600

N

CH3 CH3

CH2Br

B1858

B4279 B(OH)2

B(OH)2

B(OH)2

B(OH)2

B(OH)2 O

B4772

CH3

NH C O C CH3

Br

CH3

Br

B4700

B4640

B(OH)2

CH3

CH3 CH3

B(OH)2

B(OH)2

O(CH2)3CH3

CH3

C O C CH3

O

NH C O C CH3

B4727

B(OH)2

B(OH)2

Br

B4335

Br

140

B(OH)2

B(OH)2

CH2Br

B(OH)2

B2890

B4726

CF3

B4463

CF3

B2889

CF3

N

B3814 B(OH)2

Br

B(OH)2

B(OH)2 CH3 CH3

CH3 CH3

B(OH)2

CF3

B3022

CH3 CH3

B(OH)2

O

OCH2

F

B3056

B(OH)2

B(OH)2

OCH2

O

CH2O

(CH2)4CH3

B3779

B(OH)2

B4639

. 1/2H2SO4 NH2

B4725

B(OH)2

B(OH)2

B(OH)2

NH2

CH3

O

A2336

. H2O

NH2

C CH3

Materials Chemistry

A2818

CH3 C O C CH3 O

CH3

O(CH2)3CH3

O(CH2)3CH3

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Boronic Acids & Boronic Acid Derivatives

B3726

B3739

B2251

B2589

C2992

B(OH)2

B(OH)2

Synthetic Organic Chemistry

B(OH)2

B(OH)2

CH3 CH3

CH3 CH3 O Si

C CH3

CH3

C

Si O

B(OH)2

O

CH3 CH3

CH3 C CH3

CH3 CH3

C2570

CH3

C2967

C2926

C NH2

(CH2)3CH3

C2523

C2385

B(OH)2

B(OH)2 B(OH)2

N

N

O

Cl C NH2

O2N

C OH B(OH)2

O

C2028

C1353

C2664

C2772

B(OH)2

B(OH)2

B(OH)2

B(OH)2

B(OH)2 Cl

C OH O

O

C OH

Cl

C OH

OCH2CH3

O

C2666

C2946

C1760

C2749

C2969

F

F

C2386

C2292 B(OH)2

B(OH)2 OCH3

Cl

Cl

Cl

C2525

C2577 B(OH)2

B(OH)2

OCH3

OCH3

OH

C2665 B(OH)2

CH3

C2591 B(OH)2

B(OH)2

C2601

C2571 B(OH)2

B(OH)2

CF3

CF3

Cl

C2456

Cl

C2416 B(OH)2

B(OH)2

CF3

Cl Cl

Cl

Cl

Cl

C1473

B(OH)2

CH3

Cl CH3

CH3

Cl

C1705

B(OH)2

Cl

B(OH)2

Cl

Cl

F

C2676

F

Cl

C3056 B(OH)2

B(OH)2

B(OH)2

C1613

B(OH)2

B(OH)2

Cl

Cl

F

C3049

F

F

Cl

C2645

C2914 B(OH)2

B(OH)2

B(OH)2

Materials Chemistry

C2501

C OH

O

B(OH)2

Cl

C2031 B(OH)2

C1778 B(OH)2

B(OH)2

CN CN F

F CN

CN

CN

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

141

Boronic Acids & Boronic Acid Derivatives

Synthetic Organic Chemistry

D4670

D4263

D3783

Cl Cl

Cl

D2909

D4681

D3523 B(OH)2

B(OH)2

B(OH)2

B(OH)2

Cl

Cl

B(OH)2

B(OH)2

F

Cl Cl Cl

Materials Chemistry

B(OH)2

Cl

O(CH2)3CH3

D3357

D3044

B(OH)2

O(CH2)3CH3

Br

Cl

D2494

B(OH)2

B(OH)2

Br

D3434

D3391

Cl

Cl

D3087

F

D3521

OCH3 F

D3522

D3861

B(OH)2

OCH3

D4428

OCH3

D4194 B(OH)2

CH3

N

CH3

D3514

D3974

O

CH3

C N

CH3

CH3

CH3 CH3 CH3

CH3

B(OH)2

CH3

CH3

D3396 B(OH)2

B(OH)2 CH3

CH3 CH3

E0877

B(OH)2

CH3

CH3

D3537

D3516

D3110

B(OH)2

CH3

E0848

E0868

B(OH)2

CH3

CH3

E1124 B(OH)2

B(OH)2

B(OH)2

B(OH)2

OCH3

B(OH)2

D3633

B(OH)2

CH3O

B(OH)2

. HCl

D3517

CH3

B(OH)2

OCH3

OCH3

D4013 B(OH)2

N

B(OH)2 CH3O

D3513 B(OH)2

CH3O

OCH3

OCH3

F

D3512

B(OH)2

OCH3

B(OH)2

B(OH)2

F

F

F

D3853

B(OH)2

F

F

CH2CH3

D3081

B(OH)2

F

C N O

D3436 B(OH)2

CH2CH3

C OCH2CH3 O

O

N

C OCH2CH3

F

C OCH2CH3

OCH2CH3

O

E1107

E0723

B(OH)2 CH3CH2O

142

E0724 B(OH)2

E0725 B(OH)2

E0818 B(OH)2

B(OH)2 CH2CH3

OCH2CH3 OCH2CH3

OCH2CH3

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Boronic Acids & Boronic Acid Derivatives

E0720

F0785

F0954

F0977

B(OH)2

B(OH)2

B(OH)2

F

OH

O

B(OH)2 CH2CH3

F0941

F0876

F0919 B(OH)2

B(OH)2

C OCH3

F

F

HO

F

F0775

F0683

B(OH)2

F

OCH3

CH3

F0697

F0976

B(OH)2

B(OH)2

B(OH)2

CH3

F

CH3

F

CH3

CH3

CH3

F

F0404

F0942

F1006

B(OH)2

B(OH)2

B(OH)2

B(OH)2 F

F CH3CH2CH2

F

F0816

F0834

B1873

B(OH)2

B(OH)2

F CF3 F

F0446

H1357

CHO

O H C

H1489

H1345 B(OH)2

B(OH)2

B(OH)2

B(OH)2

B(OH)2

OCH3

CF3

F0445

CF3

F0830 B(OH)2

F

F B(OH)2

F

F0788 B(OH)2

CF3

F

F

F0361

Materials Chemistry

F0666 B(OH)2

B(OH)2

F

F

F0712

F0407

F

OCH3

OCH3

F0915

B(OH)2

B(OH)2

F

CH3O

Synthetic Organic Chemistry

B(OH)2

F0951

B(OH)2 CH2OH

CHO

H1244

O(CH2)5CH3

CHO

H1204

H1495 B(OH)2

B(OH)2

(CH2)5CH3

H1402

H1184

B(OH)2 CH3

CH2OH

H1228 B(OH)2

OH

OH

HO

CH2OH

H1185

B(OH)2

B(OH)2

OH

I0830

I0806

B(OH)2

B(OH)2

OH

I

I0887 B(OH)2

OCH

B(OH)2

CH3

CH3 CH3

CH3

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

143

Boronic Acids & Boronic Acid Derivatives

Synthetic Organic Chemistry

I0620

I0950

M2417

M2418

M2676

B(OH)2

B(OH)2

O

CH

CH3 CH3

M1905

CH3

SCH

SH

CH3

M1906

M2244 B(OH)2

B(OH)2

CH3

C OCH3

B(OH)2

CH3

O C OCH3

CH3

C OCH3

OCH3

O

M2677

M2311

M2255

B(OH)2

M2256

CH2OCH3

M1322

B(OH)2

B(OH)2

OCH3

CH3O

CH3

OCH3

M1252

M2457

M1127

M1313 B(OH)2

B(OH)2

B(OH)2

B(OH)2

M1261

CH3

OCH3

CH3 OCH3

B(OH)2

B(OH)2

CH3

M2685

B(OH)2 B(OH)2

CH2

N H

SH

M1907

O

Materials Chemistry

B(OH)2

B(OH)2

B(OH)2

B(OH)2 CH3

NO2

OCH3

M1314

CH3

CH3

OCH3

M1126

M2678 B(OH)2

B(OH)2

M1972

M1570 B(OH)2

B(OH)2

B(OH)2 SCH3

SO2CH3 CH3

M1793

CH3

SO2CH3

M1458

N0630 B(OH)2

B(OH)2

N0649

N0929

B(OH)2

B(OH)2 B(OH)2

SCH3

N1009

SCH3

N0798

N0946

N0811

N0563

B(OH)2

B(OH)2

B(OH)2

B(OH)2

B(OH)2 NO2

NO2

N0812

P1904

P1093

B(OH)2

P1974

P1984 B(OH)2

B(OH)2 F

F

F

F

O

NO2

144

F

B(OH)2

B(OH)2

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Boronic Acids & Boronic Acid Derivatives

P2158

B0857

P1358

P2290

P1968

N

B(OH)2

B(OH)2

N

(HO)2B

Synthetic Organic Chemistry

B(OH)2

B(OH)2

B(OH)2

OCH2CH2CH3

P2162

P1625

P2105

S0831

T2412

B(OH)2 CH3CH2CH2

B(OH)2

B(OH)2

N

B(OH)2

C

B(OH)2

O

T2908 B(OH)2

T2413

B(OH)2 CH3 CH3

T2362

T1773

OCF3

N CH3 CH3

T1800

OCF3

T1793

T1788

T2874 B(OH)2

CF3

T2654 B(OH)2

CH3

F

CH3

T2664

CH3 CH3O

OCH3

T2430

B(OH)2 B O

O B

Cl

F

O

O B

B O

O B

F

Cl

F

Cl

F

O B

B O

O B

O

F F

B

B O

O B

F

F

V0075 F

O B

O B

Cl

T1929

B

F

F Cl

Si(CH3)3

T1887

T1814

Cl

B

Si(CH3)3

CH3

D3435

O

B(OH)2

CH3

OCH3

CH3

T2640

F

T2663 B(OH)2

CH3

CH3

CH

F

T1960 B(OH)2

CH3

CH

F

F

T2837 B(OH)2

CH

F

F

CF3

F

B(OH)2

F

CF3

T2804

OCF3

T2574 B(OH)2

B(OH)2

B(OH)2

B(OH)2

B(OH)2

B(OH)2

Materials Chemistry

T2792

O B

F

B(OH)2

F

B O

O B

F

F

F F

F

CH CH2

Product No.

Product Name

A2453 A2818 A1942 A1907

3-Acetamidophenylboronic Acid (contains varying amounts of Anhydride) 4-Acetoxyphenylboronic Acid (contains varying amounts of Anhydride) 3-Acetylphenylboronic Acid (contains varying amounts of Anhydride) 4-Acetylphenylboronic Acid (contains varying amounts of Anhydride)

Unit Size 1g 200mg 5g 1g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

5g 1g 25g 5g

145

Materials Chemistry

Synthetic Organic Chemistry

Boronic Acids & Boronic Acid Derivatives

146

Product No.

Product Name

A2745 A1281 A1774 A2336 A1843 A2328 B4725 B3779 B3683 B4639 B4590 B3056 B2145 B2488 B2489 B2294 B2490 B3927

3-Amino-4-methylphenylboronic Acid (contains varying amounts of Anhydride) 3-Aminophenylboronic Acid Monohydrate (contains varying amounts of Anhydride) 3-Aminophenylboronic Acid Hemisulfate 4-Amylphenylboronic Acid (contains varying amounts of Anhydride) 2-Anthraceneboronic Acid (contains varying amounts of Anhydride) 9-Anthraceneboronic Acid (contains varying amounts of Anhydride) 4-(Benzyloxycarbonyl)phenylboronic Acid (contains varying amounts of Anhydride) 2-Benzyloxy-4-fluorophenylboronic Acid (contains varying amounts of Anhydride) 2-Benzyloxy-5-fluorophenylboronic Acid (contains varying amounts of Anhydride) 4-Benzyloxy-3-fluorophenylboronic Acid (contains varying amounts of Anhydride) 2-Benzyloxyphenylboronic Acid (contains varying amounts of Anhydride) 3-Benzyloxyphenylboronic Acid (contains varying amounts of Anhydride) 4-Benzyloxyphenylboronic Acid (contains varying amounts of Anhydride) 2-Biphenylboronic Acid (contains varying amounts of Anhydride) 3-Biphenylboronic Acid (contains varying amounts of Anhydride) 4-Biphenylboronic Acid (contains varying amounts of Anhydride) 4,4'-Biphenyldiboronic Acid 2,6-Bis[(2,2,6,6-tetramethyl-1-piperidinyl)methyl]phenylboronic Acid

B3022 B1886 B2860 B3600 B3814 B4463 B2889 B2890 B1858 B4279 B4335 B4726 B4772 B4700 B4640 B4727 B3726 B3739 B2251 B2589 C2992 C2570 C2967 C2926 C2523 C2385 C2501 C2028 C1353 C2664 C2772 C2666 C2946 C1760 C2914 C2749 C2645 C2969 C2386 C3056 C2292 C3049 C2525 C2577 C2665 C1705 C1613 C1473 C2591 C2601

2,4-Bis(trifluoromethyl)phenylboronic Acid (contains varying amounts of Anhydride) 3,5-Bis(trifluoromethyl)phenylboronic Acid (contains varying amounts of Anhydride) 4'-Bromo-4-biphenylboronic Acid (contains varying amounts of Anhydride) 2-(Bromomethyl)phenylboronic Acid (contains varying amounts of Anhydride) 3-(Bromomethyl)phenylboronic Acid (contains varying amounts of Anhydride) 4-Bromo-1-naphthaleneboronic Acid (contains varying amounts of Anhydride) 2-Bromophenylboronic Acid (contains varying amounts of Anhydride) 3-Bromophenylboronic Acid (contains varying amounts of Anhydride) 4-Bromophenylboronic Acid (contains varying amounts of Anhydride) 3-[(tert-Butoxycarbonyl)amino]phenylboronic Acid (contains varying amounts of Anhydride) 4-[(tert-Butoxycarbonyl)amino]phenylboronic Acid (contains varying amounts of Anhydride) 3-(tert-Butoxycarbonyl)phenylboronic Acid (contains varying amounts of Anhydride) 4-(tert-Butoxycarbonyl)phenylboronic Acid (contains varying amounts of Anhydride) 2-Butoxyphenylboronic Acid (contains varying amounts of Anhydride) 3-Butoxyphenylboronic Acid (contains varying amounts of Anhydride) 4-Butoxyphenylboronic Acid (contains varying amounts of Anhydride) 3-(tert-Butyldimethylsilyloxy)phenylboronic Acid (contains varying amounts of Anhydride) 4-(tert-Butyldimethylsilyloxy)phenylboronic Acid (contains varying amounts of Anhydride) 4-tert-Butylphenylboronic Acid (contains varying amounts of Anhydride) 4-Butylphenylboronic Acid (contains varying amounts of Anhydride) 3-Carbamoylphenylboronic Acid (contains varying amounts of Anhydride) 4-Carbamoylphenylboronic Acid (contains varying amounts of Anhydride) 3-(9H-Carbazol-9-yl)phenylboronic Acid (contains varying amounts of Anhydride) 4-(9H-Carbazol-9-yl)phenylboronic Acid (contains varying amounts of Anhydride) 4-Carboxy-3-chlorophenylboronic Acid (contains varying amounts of Anhydride) 3-Carboxy-5-nitrophenylboronic Acid (contains varying amounts of Anhydride) 2-Carboxyphenylboronic Acid (contains varying amounts of Anhydride) 3-Carboxyphenylboronic Acid (contains varying amounts of Anhydride) 4-Carboxyphenylboronic Acid (contains varying amounts of Anhydride) 3-Chloro-4-ethoxyphenylboronic Acid (contains varying amounts of Anhydride) 2-Chloro-4-fluorophenylboronic Acid (contains varying amounts of Anhydride) 2-Chloro-5-fluorophenylboronic Acid (contains varying amounts of Anhydride) 3-Chloro-2-fluorophenylboronic Acid (contains varying amounts of Anhydride) 3-Chloro-4-fluorophenylboronic Acid (contains varying amounts of Anhydride) 3-Chloro-5-fluorophenylboronic Acid (contains varying amounts of Anhydride) 4-Chloro-3-fluorophenylboronic Acid (contains varying amounts of Anhydride) 5-Chloro-2-fluorophenylboronic Acid (contains varying amounts of Anhydride) 3-Chloro-4-hydroxyphenylboronic Acid (contains varying amounts of Anhydride) 2-Chloro-4-methoxyphenylboronic Acid (contains varying amounts of Anhydride) 3-Chloro-4-methoxyphenylboronic Acid (contains varying amounts of Anhydride) 5-Chloro-2-methoxyphenylboronic Acid (contains varying amounts of Anhydride) 2-Chloro-4-methylphenylboronic Acid (contains varying amounts of Anhydride) 3-Chloro-4-methylphenylboronic Acid (contains varying amounts of Anhydride) 4-Chloro-2-methylphenylboronic Acid (contains varying amounts of Anhydride) 5-Chloro-2-methylphenylboronic Acid (contains varying amounts of Anhydride) 2-Chlorophenylboronic Acid (contains varying amounts of Anhydride) 3-Chlorophenylboronic Acid (contains varying amounts of Anhydride) 4-Chlorophenylboronic Acid (contains varying amounts of Anhydride) 2-Chloro-5-(trifluoromethyl)phenylboronic Acid (contains varying amounts of Anhydride) 4-Chloro-2-(trifluoromethyl)phenylboronic Acid (contains varying amounts of Anhydride)

(contains varying amounts of Anhydride)

Unit Size 1g 1g

1g 5g 5g 250mg 1g 1g 1g 1g 1g 1g 5g 1g 5g 5g 5g

200mg 1g 1g 5g

1g

1g 1g

5g 5g 1g 1g 1g 200mg 1g 1g 1g 1g 5g 1g 1g 1g 1g 1g 1g 1g 1g 1g 1g 1g 5g 1g 1g 1g 1g 1g 1g 1g 1g 5g 1g 1g 1g 1g 1g 5g 5g 1g 1g

5g 25g 25g 5g 1g 5g 5g 5g 5g 5g 5g 25g 5g 25g 25g 25g 1g 1g 5g 25g 1g 1g 5g 1g 5g 25g 25g 5g 5g 5g 1g 1g 5g 5g 5g 5g 25g 5g 5g 5g 5g 5g 5g 5g 5g 5g 5g 5g 25g 5g 5g 5g 5g 5g 5g 5g 5g 5g 25g 5g 5g 5g 5g 5g 25g 25g 5g 5g

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Boronic Acids & Boronic Acid Derivatives

4-Chloro-3-(trifluoromethyl)phenylboronic Acid (contains varying amounts of Anhydride) 3-Cyano-4-fluorophenylboronic Acid (contains varying amounts of Anhydride) 4-Cyano-3-fluorophenylboronic Acid (contains varying amounts of Anhydride) 2-Cyanophenylboronic Acid (contains varying amounts of Anhydride) 3-Cyanophenylboronic Acid (contains varying amounts of Anhydride) 4-Cyanophenylboronic Acid (contains varying amounts of Anhydride) 3,5-Dibromophenylboronic Acid (contains varying amounts of Anhydride) 2,4-Dibutoxyphenylboronic Acid (contains varying amounts of Anhydride) 2,3-Dichlorophenylboronic Acid (contains varying amounts of Anhydride) 2,4-Dichlorophenylboronic Acid (contains varying amounts of Anhydride) 2,5-Dichlorophenylboronic Acid (contains varying amounts of Anhydride) 2,6-Dichlorophenylboronic Acid (contains varying amounts of Anhydride) 3,4-Dichlorophenylboronic Acid (contains varying amounts of Anhydride) 3,5-Dichlorophenylboronic Acid (contains varying amounts of Anhydride) 4-(Diethylcarbamoyl)phenylboronic Acid (contains varying amounts of Anhydride) 2,3-Difluorophenylboronic Acid (contains varying amounts of Anhydride) 2,4-Difluorophenylboronic Acid (contains varying amounts of Anhydride) 2,5-Difluorophenylboronic Acid (contains varying amounts of Anhydride) 2,6-Difluorophenylboronic Acid (contains varying amounts of Anhydride) 3,5-Difluorophenylboronic Acid (contains varying amounts of Anhydride) 2,3-Dimethoxyphenylboronic Acid (contains varying amounts of Anhydride) 2,4-Dimethoxyphenylboronic Acid (contains varying amounts of Anhydride) 2,5-Dimethoxyphenylboronic Acid (contains varying amounts of Anhydride) 2,6-Dimethoxyphenylboronic Acid (contains varying amounts of Anhydride) 3,4-Dimethoxyphenylboronic Acid (contains varying amounts of Anhydride) 3,5-Dimethoxyphenylboronic Acid (contains varying amounts of Anhydride) 4-(Dimethylamino)phenylboronic Acid (contains varying amounts of Anhydride) 3-(Dimethylamino)phenylboronic Acid Hydrochloride (contains varying amounts of Anhydride) 3-(Dimethylcarbamoyl)phenylboronic Acid (contains varying amounts of Anhydride) 9,9-Dimethylfluoren-2-boronic Acid (contains varying amounts of Anhydride) 2,3-Dimethylphenylboronic Acid (contains varying amounts of Anhydride) 2,4-Dimethylphenylboronic Acid (contains varying amounts of Anhydride) 2,5-Dimethylphenylboronic Acid (contains varying amounts of Anhydride) 2,6-Dimethylphenylboronic Acid (contains varying amounts of Anhydride) 3,4-Dimethylphenylboronic Acid (contains varying amounts of Anhydride) 3,5-Dimethylphenylboronic Acid (contains varying amounts of Anhydride) 4-(Diphenylamino)phenylboronic Acid (contains varying amounts of Anhydride) 2-(Ethoxycarbonyl)phenylboronic Acid (contains varying amounts of Anhydride) 3-(Ethoxycarbonyl)phenylboronic Acid (contains varying amounts of Anhydride) 4-(Ethoxycarbonyl)phenylboronic Acid (contains varying amounts of Anhydride) 4-Ethoxy-3-fluorophenylboronic Acid (contains varying amounts of Anhydride) 6-Ethoxy-2-naphthaleneboronic Acid (contains varying amounts of Anhydride) 2-Ethoxyphenylboronic Acid (contains varying amounts of Anhydride) 3-Ethoxyphenylboronic Acid (contains varying amounts of Anhydride) 4-Ethoxyphenylboronic Acid (contains varying amounts of Anhydride) 2-Ethylphenylboronic Acid (contains varying amounts of Anhydride) 4-Ethylphenylboronic Acid (contains varying amounts of Anhydride) 2-Fluoro-4-biphenylboronic Acid (contains varying amounts of Anhydride) 3-Fluoro-5-hydroxyphenylboronic Acid (contains varying amounts of Anhydride) 5-Fluoro-2-hydroxyphenylboronic Acid (contains varying amounts of Anhydride) 4-Fluoro-3-(methoxycarbonyl)phenylboronic Acid (contains varying amounts of Anhydride) 2-Fluoro-6-methoxyphenylboronic Acid (contains varying amounts of Anhydride) 3-Fluoro-4-methoxyphenylboronic Acid (contains varying amounts of Anhydride) 4-Fluoro-3-methoxyphenylboronic Acid (contains varying amounts of Anhydride) 5-Fluoro-2-methoxyphenylboronic Acid (contains varying amounts of Anhydride) 2-Fluoro-4-methylphenylboronic Acid (contains varying amounts of Anhydride) 2-Fluoro-5-methylphenylboronic Acid (contains varying amounts of Anhydride) 3-Fluoro-4-methylphenylboronic Acid (contains varying amounts of Anhydride) 4-Fluoro-2-methylphenylboronic Acid (contains varying amounts of Anhydride) 4-Fluoro-3-methylphenylboronic Acid (contains varying amounts of Anhydride) 5-Fluoro-2-methylphenylboronic Acid (contains varying amounts of Anhydride) 2-Fluorophenylboronic Acid (contains varying amounts of Anhydride) 3-Fluorophenylboronic Acid (contains varying amounts of Anhydride) 4-Fluorophenylboronic Acid (contains varying amounts of Anhydride) 3-Fluoro-4'-propyl-4-biphenylboronic Acid (contains varying amounts of Anhydride) 2-Fluoro-3-(trifluoromethyl)phenylboronic Acid (contains varying amounts of Anhydride) 2-Fluoro-4-(trifluoromethyl)phenylboronic Acid (contains varying amounts of Anhydride) 2-Fluoro-5-(trifluoromethyl)phenylboronic Acid (contains varying amounts of Anhydride)

Unit Size 1g

1g

1g

1g 1g 5g 5g 5g 1g 5g 5g 5g 5g 1g 5g 5g 5g 1g 5g

1g

1g

1g 1g 5g 5g 5g 1g 1g 1g 1g 1g 5g 1g 1g 5g 1g 1g 1g 1g 1g 1g 1g 1g

5g 1g

1g

1g 1g 1g 1g 1g 5g 1g 1g 1g 1g 5g 1g 5g 5g 5g 1g 1g 1g 1g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

5g 1g 5g 5g 25g 25g 25g 5g 25g 25g 25g 5g 25g 5g 5g 25g 25g 25g 5g 25g 5g 5g 5g 25g 25g 25g 5g 5g 5g 5g 5g 5g 25g 5g 5g 25g 5g 5g 5g 5g 5g 5g 5g 5g 5g 5g 25g 5g 1g 5g 5g 5g 5g 5g 25g 5g 5g 5g 5g 25g 5g 25g 25g 25g 5g 5g 5g 5g

Materials Chemistry

Product Name

C2571 C2676 C2456 C2416 C2031 C1778 D4670 D4263 D3434 D2494 D3044 D3357 D3783 D2909 D4681 D3523 D3391 D3436 D3087 D3081 D3853 D3521 D3522 D3861 D3512 D3513 D4428 D4013 D4194 D3974 D3516 D3514 D3517 D3633 D3110 D3396 D3537 E0877 E0848 E0868 E1124 E1107 E0723 E0724 E0725 E0818 E0720 F0785 F0954 F0977 F0951 F0941 F0876 F0919 F0775 F0683 F0915 F0712 F0666 F0697 F0976 F0407 F0404 F0361 F0942 F1006 F0816 F0788

Synthetic Organic Chemistry

Product No.

147

Materials Chemistry

Synthetic Organic Chemistry

Boronic Acids & Boronic Acid Derivatives

148

Product No.

Product Name

F0830 F0834 B1873 F0445 F0446 H1357 H1489 H1345 H1244 H1204 H1495 H1402 H1184 H1185 H1228 I0830 I0806 I0887 I0620 I0950 M2417 M2418 M2676 M1905 M1906 M1907 M2244 M2685 M2677 M2311 M2255 M2256 M1261 M1322 M1252 M2457 M1127 M1313 M1314 M1126 M2678 M1972 M1570 M1793 M1458 N0630 N0649 N0929 N1009 N0798 N0946 N0811 N0563 N0812 P1904 P1093 P1974 P1984 P2158 B0857 P1358 P2290 P1968 P2162 P1625 P2105 S0831 T2412

4-Fluoro-3-(trifluoromethyl)phenylboronic Acid (contains varying amounts of Anhydride) 5-Formyl-2-methoxyphenylboronic Acid (contains varying amounts of Anhydride) 2-Formylphenylboronic Acid (contains varying amounts of Anhydride) 3-Formylphenylboronic Acid (contains varying amounts of Anhydride) 4-Formylphenylboronic Acid (contains varying amounts of Anhydride) 4-Hexyloxyphenylboronic Acid (contains varying amounts of Anhydride) 4-Hexylphenylboronic Acid (contains varying amounts of Anhydride) 2-(Hydroxymethyl)phenylboronic Acid (contains varying amounts of Anhydride) 3-(Hydroxymethyl)phenylboronic Acid (contains varying amounts of Anhydride) 4-(Hydroxymethyl)phenylboronic Acid (contains varying amounts of Anhydride) 4-Hydroxy-2-methylphenylboronic Acid (contains varying amounts of Anhydride) 6-Hydroxy-2-naphthaleneboronic Acid (contains varying amounts of Anhydride) 2-Hydroxyphenylboronic Acid (contains varying amounts of Anhydride) 3-Hydroxyphenylboronic Acid (contains varying amounts of Anhydride) 4-Hydroxyphenylboronic Acid (contains varying amounts of Anhydride) 4-Iodophenylboronic Acid (contains varying amounts of Anhydride) 4-Isopropoxyphenylboronic Acid (contains varying amounts of Anhydride) 3-Isopropylphenylboronic Acid (contains varying amounts of Anhydride) 4-Isopropylphenylboronic Acid (contains varying amounts of Anhydride) 4-(Isopropylthio)phenylboronic Acid (contains varying amounts of Anhydride) 3-Mercaptophenylboronic Acid (contains varying amounts of Anhydride) 4-Mercaptophenylboronic Acid (contains varying amounts of Anhydride) 3-Methacrylamidophenylboronic Acid (contains varying amounts of Anhydride) 2-(Methoxycarbonyl)phenylboronic Acid (contains varying amounts of Anhydride) 3-(Methoxycarbonyl)phenylboronic Acid (contains varying amounts of Anhydride) 4-(Methoxycarbonyl)phenylboronic Acid (contains varying amounts of Anhydride) 4-Methoxy-2,6-dimethylphenylboronic Acid (contains varying amounts of Anhydride) 4-Methoxy-3,5-dimethylphenylboronic Acid (contains varying amounts of Anhydride) 4-(Methoxymethyl)phenylboronic Acid (contains varying amounts of Anhydride) 2-Methoxy-5-methylphenylboronic Acid (contains varying amounts of Anhydride) 4-Methoxy-2-methylphenylboronic Acid (contains varying amounts of Anhydride) 6-Methoxy-2-naphthaleneboronic Acid (contains varying amounts of Anhydride) 2-Methoxyphenylboronic Acid (contains varying amounts of Anhydride) 3-Methoxyphenylboronic Acid (contains varying amounts of Anhydride) 4-Methoxyphenylboronic Acid (contains varying amounts of Anhydride) 4-Methyl-1-naphthaleneboronic Acid (contains varying amounts of Anhydride) 4-Methyl-3-nitrophenylboronic Acid (contains varying amounts of Anhydride) 2-Methylphenylboronic Acid (contains varying amounts of Anhydride) 3-Methylphenylboronic Acid (contains varying amounts of Anhydride) 4-Methylphenylboronic Acid (contains varying amounts of Anhydride) 2-(Methylsulfonyl)phenylboronic Acid (contains varying amounts of Anhydride) 4-(Methylsulfonyl)phenylboronic Acid (contains varying amounts of Anhydride) 2-(Methylthio)phenylboronic Acid (contains varying amounts of Anhydride) 3-(Methylthio)phenylboronic Acid (contains varying amounts of Anhydride) 4-(Methylthio)phenylboronic Acid (contains varying amounts of Anhydride) 1-Naphthaleneboronic Acid (contains varying amounts of Anhydride) 2-Naphthaleneboronic Acid (contains varying amounts of Anhydride) 10-(2-Naphthyl)anthracene-9-boronic Acid (contains varying amounts of Anhydride) 3-(2-Naphthyl)phenylboronic Acid (contains varying amounts of Anhydride) 4-(1-Naphthyl)phenylboronic Acid (contains varying amounts of Anhydride) 4-(2-Naphthyl)phenylboronic Acid (contains varying amounts of Anhydride) 2-Nitrophenylboronic Acid (contains varying amounts of Anhydride) 3-Nitrophenylboronic Acid (contains varying amounts of Anhydride) 4-Nitrophenylboronic Acid (contains varying amounts of Anhydride) Pentafluorophenylboronic Acid (contains varying amounts of Anhydride) 9-Phenanthreneboronic Acid (contains varying amounts of Anhydride) 4-Phenoxyphenylboronic Acid (contains varying amounts of Anhydride) 10-Phenyl-9-anthraceneboronic Acid (contains varying amounts of Anhydride) 4-(1-Phenyl-1H-benzimidazol-2-yl)phenylboronic Acid (contains varying amounts of Anhydride) Phenylboronic Acid (contains varying amounts of Anhydride) 1,4-Phenylenediboronic Acid (contains varying amounts of Anhydride) 4-Phenylnaphthalene-1-boronic Acid (contains varying amounts of Anhydride) 4-Propoxyphenylboronic Acid (contains varying amounts of Anhydride) 4-(trans-4-Propylcyclohexyl)phenylboronic Acid (contains varying amounts of Anhydride) 1-Pyreneboronic Acid (contains varying amounts of Anhydride) 4-[(1-Pyrrolidinyl)carbonyl]phenylboronic Acid (contains varying amounts of Anhydride) 9,9'-Spirobi[9H-fluorene]-2-boronic Acid 2-p-Terphenylboronic Acid (contains varying amounts of Anhydride)

Unit Size

1g

1g

1g 1g 1g 5g 1g 1g 1g 1g 5g 1g 1g 1g 1g 1g

1g

1g 1g

1g 1g

1g

1g 1g

1g 1g 1g 1g 1g 5g 5g 1g 1g 1g 5g 1g 5g 5g 5g 1g 1g 5g 5g 5g 1g 1g 1g 1g 5g 5g 1g 1g 200mg 1g 5g 1g 1g 1g 5g

5g 1g

1g

1g 25g 5g 1g 5g 1g 5g 1g 1g

5g 5g 5g 25g 5g 5g 5g 5g 5g 25g 5g 5g 5g 5g 5g 5g 5g 5g 5g 5g 5g 5g 5g 5g 25g 25g 5g 5g 5g 25g 5g 5g 25g 25g 25g 5g 5g 25g 25g 25g 5g 5g 5g 5g 5g 25g 25g 1g 5g 5g 1g 5g 25g 5g 5g 5g 25g 1g 5g 250g 25g 5g 25g 5g 25g 5g 5g 1g

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Boronic Acids & Boronic Acid Derivatives

5'-m-Terphenylboronic Acid (contains varying amounts of Anhydride) 2-[(2,2,6,6-Tetramethyl-1-piperidyl)methyl]phenylboronic Acid (contains varying amounts of Anhydride) 2-(Trifluoromethoxy)phenylboronic Acid (contains varying amounts of Anhydride) 3-(Trifluoromethoxy)phenylboronic Acid (contains varying amounts of Anhydride) 4-(Trifluoromethoxy)phenylboronic Acid (contains varying amounts of Anhydride) 2-(Trifluoromethyl)phenylboronic Acid (contains varying amounts of Anhydride) 1g 3-(Trifluoromethyl)phenylboronic Acid (contains varying amounts of Anhydride) 4-(Trifluoromethyl)phenylboronic Acid (contains varying amounts of Anhydride) 2,3,4-Trifluorophenylboronic Acid (contains varying amounts of Anhydride) 2,3,5-Trifluorophenylboronic Acid (contains varying amounts of Anhydride) 2,4,6-Trifluorophenylboronic Acid (contains varying amounts of Anhydride) 2,4,6-Triisopropylphenylboronic Acid (contains varying amounts of Anhydride) 3,4,5-Trimethoxyphenylboronic Acid (contains varying amounts of Anhydride) 2,4,6-Trimethylphenylboronic Acid 3-(Trimethylsilyl)phenylboronic Acid (contains varying amounts of Anhydride) 4-(Trimethylsilyl)phenylboronic Acid (contains varying amounts of Anhydride) 2,4,6-Triphenylboroxin 2,4,6-Tris(3,4-dichlorophenyl)boroxin 2,4,6-Tris(3,4-difluorophenyl)boroxin 2,4,6-Tris(4-fluorophenyl)boroxin 2,4,6-Tris(m-terphenyl-5'-yl)boroxin 2,4,6-Tris(3,4,5-trifluorophenyl)boroxin 4-Vinylphenylboronic Acid (contains varying amounts of Anhydride)

Unit Size

A2364

S

Cl

N

N

Cl

S

E1115

B(OH)2

O

B4063

F

N

S

B(OH)2

B(OH)2

C OC(CH3)3 O

D4567

OCH2CH3

Cl

S

B(OH)2

(HO)2B O

CH3O

N

OCH3

F0935

CH3 F

B(OH)2

D4690

F0739

N

O

B(OH)2

F

(HO)2B N

Br

D4711

F0984

(HO)2B B(OH)2

Cl

B(OH)2

B(OH)2

S

Br

D4006

S

S

O

C2066

B(OH)2

D3823

1g 1g

(HO)2B

D4057

S

1g 5g 5g 5g

N

C2288

N

D4373

B(OH)2

B2862

B(OH)2

B(OH)2

B(OH)2

1g

B4522

(HO)2B

C2589

N

S

B3307

B(OH)2

C2560

1g 1g

B(OH)2

CH3 C

B2893

S

5g 5g 1g 1g

O

Heteroarylboronic Acids

B4774

B2978

1g

1g 1g 5g 5g 25g 25g 5g 5g 5g 5g 5g 5g 1g 5g 5g 5g 25g 25g 25g 10g 100mg 5g 5g

Materials Chemistry

Product Name

T2792 T2908 T2413 T2362 T1773 T1800 T1793 T1788 T2574 T2874 T2804 T2654 T2837 T1960 T2663 T2664 T2640 D3435 T2430 T1814 T1887 T1929 V0075

Synthetic Organic Chemistry

Product No.

B(OH)2 N

F

B(OH)2

N

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

F

149

Boronic Acids & Boronic Acid Derivatives

Synthetic Organic Chemistry

F0770

F0859 F

(HO)2B N

B(OH)2

F0438

F0611

F0549

O

O H C

N

F

F0394

S

S

B(OH)2

I0803

O

H C

O

B(OH)2

M2335

B(OH)2

M2159 B(OH)2 N H

(HO)2B

O

M2035

M1850

H C

S

B(OH)2

M2029

B(OH)2 O

Materials Chemistry

F0548

N

(HO)2B N

OCH3

P2169

OCH3

P2001 B(OH)2

(HO)2B

(HO)2B

N N

P1673

O

P1594

N

CH3

S

Q0080

(HO)2B

T2621

T1772

N

150

N

T1975

T3188 B(OH)2

S

B(OH)2

B(OH)2

S

B(OH)2

B(OH)2

B(OH)2

N

S N

N

Q0087

N

N

Q0086

B(OH)2

B(OH)2

P1759 B(OH)2

B(OH)2

N

O

OCH3

(HO)2B N

S

Product No.

Product Name

A2364 B2978 B4522 B4774 B2893 B3307 B2862 B4063 C2560 C2589 C2288 C2066 D4567 D4373 D4057 D4006 D4711 D4690 D3823 E1115 F0984 F0739 F0935 F0770

5-Acetyl-2-thiopheneboronic Acid (contains varying amounts of Anhydride) Benzofuran-2-boronic Acid (contains varying amounts of Anhydride) Benzofuran-3-boronic Acid (contains varying amounts of Anhydride) Benzo[b]thiophene-3-boronic Acid (contains varying amounts of Anhydride) Benzo[b]thiophene-2-ylboronic Acid (contains varying amounts of Anhydride) 2-Bromopyridine-5-boronic Acid (contains varying amounts of Anhydride) 5-Bromo-2-thiopheneboronic Acid (contains varying amounts of Anhydride) 1-(tert-Butoxycarbonyl)-2-pyrroleboronic Acid (contains varying amounts of Anhydride) 2-Chloropyridine-3-boronic Acid (contains varying amounts of Anhydride) 2-Chloropyridine-4-boronic Acid (contains varying amounts of Anhydride) 2-Chloropyridine-5-boronic Acid (contains varying amounts of Anhydride) 5-Chloro-2-thiopheneboronic Acid (contains varying amounts of Anhydride) Dibenzofuran-4-boronic Acid (contains varying amounts of Anhydride) Dibenzothiophene-2-boronic Acid (contains varying amounts of Anhydride) Dibenzothiophene-4-boronic Acid (contains varying amounts of Anhydride) 2,6-Difluoro-3-pyridineboronic Acid (contains varying amounts of Anhydride) 2,3-Dihydrobenzofuran-5-boronic Acid (contains varying amounts of Anhydride) 2,6-Dimethoxypyridine-3-boronic Acid (contains varying amounts of Anhydride) Dithieno[3,2-b:2',3'-d]thiophene-2-boronic Acid (contains varying amounts of Anhydride) 2-Ethoxypyridine-5-boronic Acid (contains varying amounts of Anhydride) 2-Fluoro-3-methylpyridine-5-boronic Acid (contains varying amounts of Anhydride) 2-Fluoropyridine-3-boronic Acid (contains varying amounts of Anhydride) 2-Fluoropyridine-4-boronic Acid (contains varying amounts of Anhydride) 2-Fluoropyridine-5-boronic Acid (contains varying amounts of Anhydride)

CF3

Unit Size 5g

1g

1g 1g 5g 1g 1g 1g 1g 1g 1g 1g 1g 1g 1g 1g 1g 200mg 1g 5g 1g 1g

25g 1g 5g 5g 25g 5g 5g 5g 5g 5g 5g 5g 5g 5g 5g 5g 200mg 5g 1g 5g 1g 25g 5g 5g

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Boronic Acids & Boronic Acid Derivatives

5-Fluoropyridine-3-boronic Acid (contains varying amounts of Anhydride) 5'-Formyl-2,2'-bithiophene-5-boronic Acid (contains varying amounts of Anhydride) 5-Formyl-2-furanboronic Acid (contains varying amounts of Anhydride) 5-Formyl-2-thiopheneboronic Acid (contains varying amounts of Anhydride) 2-Furylboronic Acid (contains varying amounts of Anhydride) 3-Furylboronic Acid (contains varying amounts of Anhydride) 6-Indoleboronic Acid (contains varying amounts of Anhydride) 2-Methoxypyridine-3-boronic Acid (contains varying amounts of Anhydride) 2-Methoxypyridine-5-boronic Acid (contains varying amounts of Anhydride) 2-Methoxy-5-pyrimidylboronic Acid (contains varying amounts of Anhydride) 3,4-(Methylenedioxy)phenylboronic Acid (contains varying amounts of Anhydride) 5-Methyl-2-thiopheneboronic Acid (contains varying amounts of Anhydride) 9-Phenylcarbazole-2-boronic Acid (contains varying amounts of Anhydride) 9-Phenylcarbazole-3-boronic Acid (contains varying amounts of Anhydride) 3-Pyridylboronic Acid (contains varying amounts of Anhydride) 4-Pyridylboronic Acid (contains varying amounts of Anhydride) 5-Pyrimidylboronic Acid (contains varying amounts of Anhydride) Quinoline-3-boronic Acid (contains varying amounts of Anhydride) Quinoline-5-boronic Acid (contains varying amounts of Anhydride) Quinoline-8-boronic Acid (contains varying amounts of Anhydride) Thieno[3,2-b]thiophene-2-boronic Acid (contains varying amounts of Anhydride) 2-Thiopheneboronic Acid (contains varying amounts of Anhydride) 3-Thiopheneboronic Acid (contains varying amounts of Anhydride) 2-(Trifluoromethyl)pyridine-5-boronic Acid (contains varying amounts of Anhydride)

Unit Size

A2086

A2574

1g 1g 1g 1g 1g 1g 1g 1g 5g 1g 200mg 5g 1g 5g 1g 100mg 1g 200mg 1g

A2157

CH3 CH3

Alkyl & Alkenylboronic Acid Esters

CH3

O B CH C CH2

CH3

O

CH3 CH3

O

B4103

CH3 CH3

CH3

B CH2 CH3

CH3 O

O

CH3

O

C2707

CH3

O

O CH3

CH3

C2276

CH3 CH3

D3596

CH3

O

B CH2CH CH2

C3101 CH3

CH3

CH3 CH3

CH3

O

O

CH3

CH3

O

CH3

O

CH3

O

B

B

B CH2Br

B CH2 B

O

O

CH3

B3199

CH3

O

CH3 B CH2CH CH2

CH3

B3448

5g 1g

O

CH3

CH3

CH3

D3738

D3649

E1116 CH3

CH3 CH3

O CH2 CH B

B CH3

O

O(CH2)3CH3 O(CH2)3CH3

CH2 CHCH2 B

OCH(CH3)2 OCH(CH3)2

BrCH2 B

E1074

M2071 CH3

CH3

O

OCH(CH3)2

CH3

O

B CH2CH3

T2297 CH3

CH3

O B C CH

CH3

OCH(CH3)2

CH3

CH3

CH3

5g 1g 5g 5g 5g 5g 1g 5g 5g 5g 25g 5g 1g 25g 25g 5g 1g 5g 200mg 1g 1g 25g 5g 1g

Materials Chemistry

Product Name

F0859 F0548 F0611 F0549 F0394 F0438 I0803 M2159 M2029 M2335 M2035 M1850 P2169 P2001 P1673 P1594 P1759 Q0080 Q0087 Q0086 T2621 T1772 T1975 T3188

Synthetic Organic Chemistry

Product No.

O CH3

CH3

O B CH2

CH3

O CH3

CH3

O

CH3

O

B CH CH2

OCH3

CH3

Product No.

Product Name

A2086 A2574 A2157 B3448 B4103 B3199

2-Allenyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 2-Allyl-5,5-dimethyl-1,3,2-dioxaborinane (stabilized with Phenothiazine) 2-Allyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (stabilized with Phenothiazine) 2-Benzyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Bis[(pinacolato)boryl]methane 2-(Bromomethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

Unit Size 1g 1g 1g 1g 1g 1g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

5g 5g 5g 5g 5g 5g

151

Materials Chemistry

Synthetic Organic Chemistry

Boronic Acids & Boronic Acid Derivatives

Product No.

Product Name

C2707 C3101 C2276 D3596 D3738 D3649 E1116 E1074 M2071 T2297

2-(1-Cyclohexenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 2-Cyclohexyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 2-Cyclopropyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Dibutyl Vinylboronate (stabilized with Phenothiazine) Diisopropyl Allylboronate Diisopropyl (Bromomethyl)boronate 2-Ethyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 2-Ethynyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 2-(4-Methoxybenzyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 4,4,5,5-Tetramethyl-2-vinyl-1,3,2-dioxaborolane (stabilized with Phenothiazine)

Unit Size

B4633 CH3

Arylboronic Acid Esters

O

CH3

O

CH3 CH3

B4588

CH3 O B O CH3

O B O

CH3 CH3 CH3 CH3

B3501

CH3 CH3

CH3

CH3

O

O

CH3

CH3

O

CH3

CH3 O B OCH (CH ) 3 2 9 CH3

O B (CH2)9CH3O

CH3 CH3

Fe

CH3 CH3

O

B

O

O

CH3 CH3

CH3

CH3 O

O B

B

O CH3

O

NC CH3

B

CH3

O

D3601

O

O

CH3

B

N

CH2CH3

CH3

CH2CH3

CH3

CH3

CH3

O

CH3 O

CH3CH2O C O CH3 B CH3 O

O

CH3

O

O

CH3

O

CH3

B O

CH3

O

CH3

O

CH3

B

CH3

O

CH3

O

B Cl

O

Cl

CH3

CH3

O

N

CH3

CH3 CH3

CH3

O

CH3

O

CH3 OH

B

CH3

CH3

I0653

M2665 O

CH3 CH3

O

CH3

O

O

OH

OH

CH3

CH3 CH3

B

B

Cl

D2853

B CH3

CH3 CH3

O

CH3

Cl

CH3

O

(CH2)7CH3 O

O

CH3

B

F CH3

O CH3(CH2)7

CH3

D4201

D3832

CH3

CH3

B

CH3

CH3

NC

H1280

O

Br

D4575

B

F0531

CH3

O B

CH3

CH3

E0667

CH3 CH3

CH3

CH3 O

Cl B

D3533

O

CH3

O

B

CH3

CH3

C2004

CH3

CH3

O

CH3

CH3

Br

O

CH3

CH3

CH3

CH3 CH3

O CH3(CH2)5 CH3

B

B O

D4195

O

CH3

CH3

CH3 O B (CH2)5CH3 O

B

B4771

C2621

NC

CH3

CH3 CH3

CH3

B3582

CH3 O

CH3

C2823

O

CH3

CH3

CH3

B2828

CH3 CH3

C2993

(CH2)11CH3 O

O CH3(CH2)11 CH3

CH3 CH3

CH3

B

B

O O

B

CH3

CH3 O

O

CH3

CH3

B4029

CH3 CH3

CH3 CH3

O

152

CH3 CH3

O B O

CH3

B

B

B4624

B3956

B

CH3

CH3 B

5g

B3151

O

CH3

B4166

1g

B3019

CH3

1g 5g 5g 5g 5g 5g 5g 1g 5g 25g

1g 1g 1g 1g 1g 1g 200mg

I

C OCH3

B CH3

B

O

O CH3

CH3 CH3 CH3

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Boronic Acids & Boronic Acid Derivatives

N0824

P1855 CH3

NO2

CH3

O

CH3

B

O CH3

CH3 CH3 B CH3

O B

C H

O

O

B

O

O

CH3

CH3

B

CH3

CH3

O

CH3

O

CF3

OH

O

CH3

O

CH3

O

CH3

O

CH3

B

O

CH3

T2888 CH3

CH3 O

CH3

O

CH3

CH3

O

CH3

O

CH3

O

B CH3

O C CH3

CH3

T3219

O2N

CH2Br

B

CH3

O

O CH3

B

CH3

CH3

T2428

B

B

B

CH3

O

CH3

O

T3089

CH3 CH3

O

T3224

B

CH3

T3261

CH3

CH3

OH

O

CH3

T3103

O

CH3

T1954

B CH3

CH3

C OH

O

B

O

CH3

CH3

CH3 O

O

CH3

CH3 CH3

N1006 CH3

T2945

CH3 CH3 CH3

O

CH3

CH3

NH2

CH3

B

B

B CH3

T3218

C OH

O

HO

O

OH

CH3

O

Materials Chemistry

CH3

CH3

B

O

T2841

T1953 CH3

CH3

O

CH3

CH3

T1952

CH3

CH3

B

C CH3

CH3

CH3 CH3 CH3

CH3

T3031

CH3

NH2

O

O

O

CH3

NH

T3162

OCH3

O

O

O

CH3

O

CH3

CH3

CH3

O

CH3

T2923

CH3

O

CH3

T3196

CH3

CH3

B

O

CH3

T1951 CH3

CH3

O

NH2

B

T3028

Synthetic Organic Chemistry

CH3 CH3

T1950

O

O CH3

CH3 CH3 CH3

CH3

CH3 CH3

O

CH3

O

CF3 B

CH3

Product No.

Product Name

B4633 B3019 B3151 B4166 B4588 B4624 B4029 B3582 B3501 B3956 B2828 B4771 C2004 C2993 C2823 C2621

1,4-Benzenediboronic Acid Bis(pinacol) Ester 2-(4-Biphenylyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 4,4'-Bis(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)biphenyl 4,4'-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)biphenyl 2,7-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-didecylfluorene 2,7-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-didodecylfluorene 2,7-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-dihexylfluorene 2,7-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-di-n-octylfluorene 1,1'-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)ferrocene 2,7-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrene 2-(2-Bromophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 2-(4-Bromophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 2-(2-Chlorophenyl)-5,5-dimethyl-1,3,2-dioxaborinane 2-Cyanophenylboronic Acid 1,3-Propanediol Ester 2-(2-Cyanophenyl)-5,5-dimethyl-1,3,2-dioxaborinane (This product is only available in Japan.) 2-(2-Cyanophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

D4575 D4201 D3601 D4195 D3533 D3832

2-(3,5-Dichlorophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 2,6-Dichloro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol N,N-Diethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline 5,5-Dimethyl-2-phenyl-1,3,2-dioxaborinane 2-(3,5-Dimethylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane N,N-Dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline

(This product is only available in Japan.)

Unit Size 5g

1g

1g 1g 1g 1g 1g 1g 1g 1g 1g 1g 5g 1g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

25g 5g 1g 5g 1g 1g 1g 1g 5g 5g 5g 5g 1g 5g 5g 5g 5g 5g 5g 25g 5g 5g

153

Materials Chemistry

Synthetic Organic Chemistry

Boronic Acids & Boronic Acid Derivatives

Product No.

Product Name

D2853 E0667 F0531 H1280 I0653 M2665 N0824 P1855 T1950 T3028 T1951 T3196 T2923 T3162 T2841 T2945 T3031 T1952 T1953 T1954 T3224 T3218 N1006 T3089 T3219 T2888 T3103

2,6-Dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol Ethyl 2-(5,5-Dimethyl-1,3,2-dioxaborinan-2-yl)benzoate 2-(2-Fluorophenyl)-5,5-dimethyl-1,3,2-dioxaborinane 2-(Hydroxymethyl)phenylboronic Acid Cyclic Monoester 2-(2-Iodophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Methyl 3-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)benzoate 2-Nitro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline 2-Phenyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 4'-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)acetanilide 3-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)aniline 4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)aniline 4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)anisole 4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)benzaldehyde 3-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)benzoic Acid 4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)benzoic Acid 4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)benzyl Bromide 4'-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)biphenyl-4-ol 2-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)phenol 3-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)phenol 4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)phenol 4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl Acetate 4,4,5,5-Tetramethyl-2-(1-naphthyl)-1,3,2-dioxaborolane 4,4,5,5-Tetramethyl-2-(2-nitrophenyl)-1,3,2-dioxaborolane 4,4,5,5-Tetramethyl-2-(3-perylenyl)-1,3,2-dioxaborolane 4,4,5,5-Tetramethyl-2-(m-tolyl)-1,3,2-dioxaborolane 4,4,5,5-Tetramethyl-2-(p-tolyl)-1,3,2-dioxaborolane 4,4,5,5-Tetramethyl-2-[4-(trifluoromethyl)phenyl]-1,3,2-dioxaborolane

Unit Size

T3261 T2428

4,4,5,5-Tetramethyl-2-[3-(triphenylen-2-yl)phenyl]-1,3,2-dioxaborolane 2-[2-(Trifluoromethyl)phenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

1g

1g 1g 5g 1g 1g 5g 1g 1g 1g 1g 1g 1g 1g 1g 1g 1g 200mg 1g 1g 1g 200mg

(This product is only available in Japan.)

B4364

B4158

CH3

Heteroarylboronic Acid Esters

CH3

O O

CH3

N

CH3

N

S S

O B O

CH3 CH3

N

CH3 CH3

B3200 CH3

CH3 CH3

O

CH3

O

B

S

O

CH3

O

CH3

CH3

CH3

D4290

CH3

O B

B

S

CH3

S

O

S

Br

CH3

CH3

O

CH3

CH3

S

CH3

M2650

S

O

O

CH3

O

B CH3

OCH3 N

CH3

O CH3

N

O

O (CH2)7CH3

CH3

CH3

O

B

CH3 CH3

S

(CH2)5CH3

O B

CH3

O

S

O CH3

CH3

O0439

O0410 CH3(CH2)7

CH3

O O

O

O

H1294

CH3

M2681

N

CH3

CH3

CH3

CH3

O B

CH3

CH3

CH3 CH3

CH3

O B

CH3

B

CH3 N

N

CH3

154

CH3

O CH3 N C O C CH3

B

CH3

CH3

O

CH3 CH3(CH2)7

CH3

CH3

Br

CH3

CH3 O

H1298

B

M2339

CH3

CH3

N

O

CH3 CH3

CH3

CH3

CH3

(CH2)11CH3

O

CH3

B

B O CH3 CH3 CH3

D3772

CH3(CH2)5 B

O

CH3

O0428

CH3

B

O

CH3

D4291

CH3(CH2)11

B4051 CH3

CH3 CH3

CH3

B3749

N S

O

CH2

B3363

CH3 CH3 CH3 O B

O

CH3 O B O CH3

CH3

B

5g 1g 5g

B3573

CH3

CH3

5g 1g 1g 5g 1g 5g 1g 25g 1g 5g 5g 25g 5g 5g 1g 5g 5g 5g 5g 5g 5g 5g 5g 1g 5g 5g

CH3

O

N

B

N

O

CH3

CH3

CH3 CH3

O

CH3

O

CH3 B

CH3

N (CH2)7CH3

O

CH3

O

CH3

B

CH3 CH3

CH3

CH3

O

B

S

O CH3

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Boronic Acids & Boronic Acid Derivatives

O0411

P2277

T3215

O

CH3

O

(CH2)7CH3 B

S

CH3

O

CH3 CH3

T3117

O

B

O

B

CH3

CH3

N

N

N

CH3 CH3

CH3

O

O

B

O

CH3

N O

CH3

CH3

Synthetic Organic Chemistry

CH3 CH3

T2518

CH3

CH3

S

O

CH3

B

S N H

CH3

CH3

O

CH3

CH2CH2CH3

T3236

I0590

I0739 CH3

CH3 S O

B

CH3

CH3 CH3

CH3

O

B

O

O

CH3 B

N H

N

T2345 CH3

CH3

CH3

O

CH3 CH3

CH3

O

CH3

O

CH3

O

B

B N H

N

N

CH3

T2924 CH3

CH3 O

CH3

B O

CH3

Materials Chemistry

T2349

CH3

CH3

O

CH3 O

T2756 CH3

CH3

O

CH3

O

B

N

S

CH3

CH3

Product No.

Product Name

B4364 B4158 B3573 B3363 B3200 B3749 B4051 D3772 D4290 D4291 O0428 H1298 H1294 M2650 M2339 M2681 O0439 O0410 O0411 P2277 T3215 T2518 T3117 T3236 I0590 I0739 T2756 T2345 T2349 T2924

1-Benzyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrazole 1g 5g 2,6-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzo[1,2-b:4,5-b ']dithiophene 1g 4,7-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,1,3-benzothiadiazole 1g 5,5'-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,2'-bithiophene 5g 5-Bromo-5'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,2'-bithiophene 1g 2-Bromo-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine 1g 5g 1g 1-(tert-Butoxycarbonyl)-1,2,3,6-tetrahydro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine 3,5-Dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)isoxazole 1g 5g 3-Dodecyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene 1g 5g 4-Dodecyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene 1g 5g 9-(9-Heptadecanyl)-2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)carbazole 200mg 1g 3-Hexyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene 1g 5g 25g 4-Hexyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene 5g 2-Methoxy-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine 1g 5g 1-Methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrazole 1g 5g 1-Methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrazole 1g 5g 200mg 9-n-Octyl-2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)carbazole 3-n-Octyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene 1g 5g 1g 5g 4-n-Octyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene 1-Propyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrazole 1g 5g 1-(Tetrahydropyran-2-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrazole 1g 5g 5-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-2,2'-bithiophene 1g 5g 25g 3-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)carbazole 1g 5g 4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)dibenzothiophene 1g 5g 1g 5g 5-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole 4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)isoquinoline 1g 5g 4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)pyrazole 1g 5g 3-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine 1g 5g 25g 4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine 1g 5g 2-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene 1g 5g

Unit Size

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

155

Chiral Building Blocks

Synthetic Organic Chemistry

Chiral Building Blocks

A1299

A1334

O

A1648

A2153

. HCl

NH2

A0826

HO

A1688

O

A1043

OH

. HBr

O C OH

NH2

NH2

A1438 O

C OH H 2N

B1756

C OH O NH

O CH3

OH

F

F N

O

C OH

N

C OH

C OH

C OC(CH3)3

O

O

B4083

C1584

Boc

N Boc

O

C OCH2 O

Boc

O

O

C1377 O

OH

Cl NH2

C OH

C OC(CH3)3

C2109 O

C OH N

O N

OH

N

O

O

B3700

O OH

N

O

Boc

NH C OC(CH3)3

B4141

HO

OH

N

O

C1612

OH

F F

O

C OH

C OC(CH3)3

B4202

O

B1635

O

OH Br

NH C OC(CH3)3

B3178

CH3

O

C

B3539

OH

CH3 O

OH

O

Br

B3177

HO

B3538

Br

B4005 O

O

O CH3

NH2

O

B1757

OH OH

B4142

C OH NH C

OH NH2

O

B1120

OH NH

. HCl

CH3

NH2

A2286

C OH

O

O

156

Br

NH2

O

B1121

OH NH2

OH NH2

CH2

O

O OH

A1689

O CH3

HO

NH2

OH

A1377

O OH

O

S

A1450

O OH

O

O

CH3

CH3

A1457

O CH2

O

OH CH3

O

Materials Chemistry

O

O CH3

Carboxylic Acids

A1647

. HCl

CH3

O OH

Cl

CH3

OH Cl

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Chiral Building Blocks

C1663

C2738

C1365 CH3

O OH

Cl

Cl

C1655

OH Cl

CH3

O

C OH

C OH

C OH

C OH

O

O

O

CH3

O

O

O

. HCl

NH2

O

H2N

OH

. 2HCl

NH2

CH3

H 2N

D3491

D1354 D3492

D1398 D3826 O

O

HOOC

O C

OCH3

HOOC

O C

OCH3

HOOC

O C

OCH3

HOOC

O C

OCH3

O

Ph

O O

O

HO

O

Ph OH . H2O

O

Ph

O

O

O

HO

OH . H2O O

O

O

D2539

D4375

D3677

D2702

O

CH3

C OH

CH3

CH3O

OH NH2

NH

CH3O

D2686

(CH3)3C

O O

O

(CH3)3C

HO

C OH

. HCl

O OH

O

C(CH3)3

O

O

HO

OH O

O

Ph O

O

O

D1387 O

p-Tol

E0993

O

E0994

O

O p-Tol

O

HO

OH O

OH O

H C O

N

O

N

O

N

O

N

O

O

O

H0937

HO

O

NH2

H0933

I0589 O

O OH NH2

O

OH

CH3

OH

L0026 O

OH OH

O OH

I0395

O

N

O HO

NH

HO

H1339

OH

NH2

O

O

HO

O OH

OH

N H

OH

O

HO HN

H0758

F

NH

OH

H1224

O

C Cl

O

NH

O

G0265 O

CH2CH3

O

p-Tol

O

O

F0721

F0818

CH2CH3

O

HO

p-Tol

O

O

C(CH3)3

O

O

D1417

. HCl

OH NH2

O

O

OH

O OH

O

D3490

H2N

D1573

O

HO

O

O

OH NH2

D0083

CH3

O OH

O

D1377

O

O

HO

O

C2569

O

D1386 O

OH

Cl

Materials Chemistry

D2636

N H

OH CH3

OH Cl

D3825

CH3

Cl

C1954

O CH3

OH

Cl

C1953

O

O

O

CH3

OH

OH

C1373

CH3

CH3

O

CH3

OH

OH

C1371

Synthetic Organic Chemistry

O

C1372

N H

OH O

N H

OH O

CH3

OH CH3

OH

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

157

Chiral Building Blocks

Synthetic Organic Chemistry

L0144

M0021

M0022

M0661 O

O O

O CH3

HO

OLi

M1366

HO

OH O

OH

OH

O

M1021

M0829

M1228

O CH3

C OH

OH

M1229 O

C OH

OH

HO

N0327

HO

OH

O0281

O0276

N H H

O0064

H2N

P1288

OH

C OH

O

O

O

O

P1219 O

CH3

C OH

P1830

HO

OH

O

O

N H

OH

N0678

Q0009

O

O

C OH

C OH

N H

N H

T1740

T0026 OH

OH O

OH

OH

O

HO

O

HO

OH

OH O

OH

OH

T1515

O O

C OH

N H

T0025

HO C OH

T0219 O

C OH

O

C OH

O

HO

T1741

O

P1404

O

OH

N0654

OH

NH2

P0936 O

OH

OH

OH

C OH

. HCl

NH2

O

P1168

158

H2N

P1981

NH2

O

. 2HCl

NH2

O O

O OH

C OH

P0820

O O

OH NH2

O O

NH2

CH3

NH2

H OH

NH2

OH

O0089

O CH3

O

CH3

CH3

O0370

O

OH

O OH

O

CH3

N0686

O

N0303

O OH

O

CH3

N0673

O

C OH

CH3

O

HO

CH3O

HO

M1227

O

CH3

CH3O

O

O

M1226

C OH

OH

M0830

CH3O

HO

C OH

OH

O CH3

HO

O

CH3O

Materials Chemistry

M0662

C OH

C OH NH

T1900 O

O

HO C

NH S

CF3

OH

HO CH3

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Chiral Building Blocks

T1901

Synthetic Organic Chemistry

O CF3

OH

HO CH3

Product Name

A1299 A1334 A1647 A1648 A2153 A1457 A1450 A1377 A0826 A1688 A1689 A2286 A1438 A1043 B1121 B1120 B4142 B4005 B1756 B1757 B3538 B3539 B4202 B3177 B3178 B1635 B4141 B3700 B4083 C1584 C1612 C2109 C1377 C1663 C2738 C1365 C1372 C1371 C1655 C1373 C1953 C1954 C2569 D3825 D2636 D1386 D0083 D1573 D1377 D3490 D3491 D1398 D3826 D1354 D3492 D2539 D4375 D3677

(S)-(-)-2-Acetoxypropionic Acid 5g 25g (S)-(-)-3-(Acetylthio)-2-methylpropionic Acid 5mL 25mL 200mg 1g D-2-Allylglycine Hydrochloride 200mg 1g 5g L-2-Allylglycine Hydrochloride 1g 5g D-2-Aminoadipic Acid 1g 5g L-2-Aminoadipic Acid (S)-(+)-2-Amino-4-bromobutyric Acid Hydrobromide 1g 5g (R)-(-)-2-Aminobutyric Acid 1g 5g 1g 5g (S)-(+)-2-Aminobutyric Acid (1R,2R)-2-Aminocyclohexanecarboxylic Acid 100mg (1S,2S)-2-Aminocyclohexanecarboxylic Acid 100mg (1S,3R)-3-Aminocyclohexanecarboxylic Acid 200mg (S)-(-)-4-Amino-2-hydroxybutyric Acid 5g 25g 100mg 1g L-Azetidine-2-carboxylic Acid (+)-cis-2-Benzamidocyclohexanecarboxylic Acid 5g (-)-cis-2-Benzamidocyclohexanecarboxylic Acid 5g (S)-Benzylsuccinic Acid 5g 25g 5g (R)-2-Bromo-3-methylbutyric Acid (R)-(+)-2-Bromopropionic Acid 5g 25g (S)-(-)-2-Bromopropionic Acid 5g 25g (1R,3S)-3-(tert-Butoxycarbonylamino)cyclohexanecarboxylic Acid 1g (1S,3R)-3-(tert-Butoxycarbonylamino)cyclohexanecarboxylic Acid 1g 200mg 1g (S)-1-(tert-Butoxycarbonyl)-4,4-difluoro-2-pyrrolidinecarboxylic Acid (2S,4R)-1-(tert-Butoxycarbonyl)-4-fluoro-2-pyrrolidinecarboxylic Acid 200mg 1g (2S,4S)-1-(tert-Butoxycarbonyl)-4-fluoro-2-pyrrolidinecarboxylic Acid 200mg 1g trans-N-(tert-Butoxycarbonyl)-4-hydroxy-L-proline 5g N-(tert-Butoxycarbonyl)-4-oxo-L-proline 1g 5g 1g 5g (S)-1-(tert-Butoxycarbonyl)-2-piperidinecarboxylic Acid N-(tert-Butoxycarbonyl)-L-pyroglutamic Acid 5g 25g (3S)-2-Carbobenzoxy-1,2,3,4-tetrahydroisoquinoline-3-carboxylic Acid 5g 3-Chloro-L-alanine Hydrochloride 1g 5g (R)-2-Chlorobutyric Acid 1g 5g 1g 5g (S)-2-Chlorobutyric Acid 2-Chloro-D-mandelic Acid 1g 5g 2-Chloro-L-mandelic Acid 5g 25g (S)-2-Chloro-3-methylbutyric Acid 1g 5g (2S,3S)-2-Chloro-3-methylvaleric Acid 1g 5g 1g 5g (S)-2-Chloro-4-methylvaleric Acid (R)-(+)-2-Chloropropionic Acid 1g 5g 25g (S)-(-)-2-Chloropropionic Acid 1g 5g 25g (1R,2R)-1,2-Cyclohexanedicarboxylic Acid 1g 5g (1S,2S)-1,2-Cyclohexanedicarboxylic Acid 1g 5g 1g 5g L-2-Cyclohexylglycine 3,4-Dehydro-L-proline 100mg 1g (+)-Diacetyl-D-tartaric Acid 5g (-)-Diacetyl-L-tartaric Acid 25g (S)-(+)-2,4-Diaminobutyric Acid Dihydrochloride 1g 100mg 1g (R)-(-)-2,3-Diaminopropionic Acid Hydrochloride (S)-(+)-2,3-Diaminopropionic Acid Hydrochloride 100mg 1g (+)-Di-p-anisoyl-D-tartaric Acid 25g (-)-Di-p-anisoyl-L-tartaric Acid 25g (+)-Dibenzoyl-D-tartaric Acid Monohydrate 25g 500g 25g 250g (+)-Dibenzoyl-D-tartaric Acid (-)-Dibenzoyl-L-tartaric Acid Monohydrate 25g 500g (-)-Dibenzoyl-L-tartaric Acid 25g 250g 5g 25g D-(-)-2-(2,5-Dihydrophenyl)glycine (S)-(-)-6,7-Dimethoxy-1,2,3,4-tetrahydroisoquinoline-3-carboxylic Acid Hydrochloride 1g 5g 1g 5g (S)-(+)-2,2-Dimethylcyclopropanecarboxylic Acid

Unit Size

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

Materials Chemistry

Product No.

159

Materials Chemistry

Synthetic Organic Chemistry

Chiral Building Blocks

Product No.

Product Name

D2702 D2686 D1417 D1387 E0993 E0994 F0818 F0721 G0265 H1224 H0937 H1339 H0758 H0933 I0589 I0395 L0026 L0144 M0021 M0022 M0662 M0661 M1366 M1021 M0830 M0829 M1228 M1229 M1226 M1227 N0327 N0303 N0673 N0686 O0370 O0089 O0064 O0281 O0276 P0820 P1288 P1981 P1168 P1219 P0936 P1830 P1404 N0654 N0678 Q0009 T0026 T0025 T1740 T1741 T1515 T0219 T1900 T1901

(+)-Dipivaloyl-D-tartaric Acid (-)-Dipivaloyl-L-tartaric Acid (+)-Di-p-toluoyl-D-tartaric Acid (-)-Di-p-toluoyl-L-tartaric Acid (R)-(-)-α-[[(4-Ethyl-2,3-dioxo-1-piperazinyl)carbonyl]amino]benzeneacetic Acid (R)-(-)-α-[[(4-Ethyl-2,3-dioxo-1-piperazinyl)carbonyl]amino]-4-hydroxybenzeneacetic Acid trans-4-Fluoro-L-proline O-Formyl-D-mandeloyl Chloride (S)-(-)-2-Guanidinoglutaric Acid D-Homoserine (R)-(+)-2-(4-Hydroxyphenoxy)propionic Acid (S)-2-Hydroxy-4-phenylbutyric Acid 4-Hydroxy-D-(-)-2-phenylglycine (S)-(+)-2-Hydroxy-4-phthalimidobutyric Acid (R)-(+)-Indoline-2-carboxylic Acid (S)-(-)-Indoline-2-carboxylic Acid 1g L-Leucic Acid Lithium L-Lactate D-(+)-Malic Acid 25g L-(-)-Malic Acid 25g D-(-)-Mandelic Acid L-(+)-Mandelic Acid (R)-(-)-2-Methoxy-2-(1-naphthyl)propionic Acid (S)-(+)-2-(6-Methoxy-2-naphthyl)propionic Acid (R)-(-)-α-Methoxyphenylacetic Acid 100mg (S)-(+)-α-Methoxyphenylacetic Acid (R)-(-)-2-Methylglutaric Acid (S)-(+)-2-Methylglutaric Acid (R)-(+)-Methylsuccinic Acid (S)-(-)-Methylsuccinic Acid D-Norleucine 100mg L-Norleucine 1g D-Norvaline L-Norvaline (2S,3aS,7aS)-Octahydro-1H-indole-2-carboxylic Acid L-Ornithine Dihydrochloride L-Ornithine Monohydrochloride (R)-(-)-5-Oxotetrahydrofuran-2-carboxylic Acid (S)-(+)-5-Oxotetrahydrofuran-2-carboxylic Acid D-2-Phenylglycine L-2-Phenylglycine D-(+)-3-Phenyllactic Acid L-(-)-3-Phenyllactic Acid (R)-(-)-2-Phenylpropionic Acid (S)-(+)-Phenylsuccinic Acid D-Pipecolic Acid L-Pipecolic Acid (R)-(-)-3-Piperidinecarboxylic Acid (S)-(+)-3-Piperidinecarboxylic Acid D-(-)-Quinic Acid D-(-)-Tartaric Acid L-(+)-Tartaric Acid (R)-(+)-Tetrahydrofuran-2-carboxylic Acid (S)-(-)-Tetrahydrofuran-2-carboxylic Acid 1g (S)-(-)-1,2,3,4-Tetrahydroisoquinoline-3-carboxylic Acid L-Thioproline (R)-3,3,3-Trifluoro-2-hydroxy-2-methylpropionic Acid (S)-3,3,3-Trifluoro-2-hydroxy-2-methylpropionic Acid

Unit Size

A2124

A1101

Esters O

160

O

O

O

C CH3

O O

1g 1g 25g

1g 5g 5g 100g 100g 25g 25g 1g 1g

5g 1g 1g 5g 1g 1g 1g 25g 1g 1g 25g 25g 1g 1g 1g 5g 1g 1g 1g 5g 25g 25g 5g 5g 5g 25g

5g 25g 250g 250g 5g 5g 50mg 25g 100mg 5g 5g 5g 500g 5g 1g 5g 25g 25g 25g 500g 500g 250g 100mg 500g 5g 5g 5g 5g 25g 5g 10g 5g 25g 5g 5g 5g 250g 5g 5g 500g 100g 5g 5g 5g 1g 25g 5g 5g 5g 25g 500g 500g 25g 25g 25g 500g 1g 1g

L0161

O O

1g 5g 25g 25g 1g 1g

O

O

C CH3

O CH3

O OH

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Chiral Building Blocks

M1354

M1355

B3987

N

OH

OH

B4083

Boc

B4026

N

O

Boc

N H

O

O

OH

O

OH

T1387

O O

OH

T0621

CH3

O

O

CH3

CH3

O

CH3

O

O

CH3

M1230

O O

CH3

O

O

O O

M1347 C OCH3

O

O

O

CH3

CH3 CH3

O CH3O

OCH3 O

M1232

OH

P1189 O

O

O CH3O

OCH3 O

O

CH3O

CH3O

CH3

T1659

OCH3 O

T0006

CH3O

CH3

E0948

C OCH3 O

OCH3 O

O

CH3O C

O

O OCH3

OH

CH3

OH

O

O

M1231

CH3

OH

C OCH3 CH3O C O

OH

OH

O

O

CH3O C

CH3

M1343

O

I0447

OH

CH3 O

OH

CH3 O

OH

CH3

O

I0474

CH3 O

CH3

OH

O OH

OH

O

CH3

OC(CH3)3

OH

T0003

O CH3

O

O

(CH3)3CO

T1195

O O

CH3

CH3

CH3

OH

O O

O

O

M1348

O O(CH2)3CH3

O

OH O

O H

CH3

O

D3898

H

HO

CH3

C O C CH3

N

O

T1671

O

M1351

CH3(CH2)3O

Boc

O

CH3O C

Materials Chemistry

T0005

OC(CH3)3

OCH3

N

O

H1418 HOH2C

OH

O

OCH3

Synthetic Organic Chemistry

O

O

B1755

HO

HO

O

O

B3843

O

CH3

CH3

E0940

E0469

O OH

O

CH3O

OH OCH3

O

OCH3 O

OH

C OCH2CH3

O

CH3O

N

OH

E0450

H0904

O

CH3CH2 O

N0655

N H

CH3

CH3

M1273

N0679

O O

CH3

O

C OCH2CH3

C OCH2CH3

CH3

H0958

SO3

O CH3

CH3

HOCH2

CH3

L0115

O CH3

O OH

OH

T1241

O

O O

OH

OH

N H

M1344 O

O

OCH2CH3

N CH3CH2 O

O

CH3

L0162

OCH2CH3

N

Boc

C O C CH3 O

OCH2CH3

N

O

CH3

O

O

O

O

CH3

CH3

O

O

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

161

Chiral Building Blocks

Synthetic Organic Chemistry

A1383

B2139

O CH3

O S

Br

CH3

O CH3 CH3

M1349

O

HO

HO

M1350

O

CH3

OCH3

OCH3

O

OCH3 OH

M2198

OCH3

CH3

OH

P0011

O

O OCH3

N H

OCH3

CH3

OH

CH3

O

O

Product No.

Product Name

A2124 A1101 L0161 M1354 M1355 B3987 B3843 B1755 B4083 B4026 H1418 T1671 D3898 T0005 M1351 M1348 T1195 T0003 T1387 T0621 I0474 I0447 M1347 M1343 M1230 M1231 M1232 P1189 T1659 T0006 E0948 E0940

(+)-O-Acetyl-D-malic Anhydride (-)-O-Acetyl-L-malic Anhydride Benzyl (S)-(-)-Lactate Benzyl D-(-)-Mandelate Benzyl L-(+)-Mandelate N-(tert-Butoxycarbonyl)-cis-4-hydroxy-L-proline Methyl Ester N-(tert-Butoxycarbonyl)-trans-4-hydroxy-L-proline Methyl Ester (S)-(-)-3-tert-Butoxycarbonyl-4-methoxycarbonyl-2,2-dimethyl-1,3-oxazolidine N-(tert-Butoxycarbonyl)-L-pyroglutamic Acid tert-Butyl L-Pyroglutamate (-)-Corey Lactone Dibenzyl L-Tartrate Di-tert-butyl L-(+)-Tartrate Dibutyl L-(+)-Tartrate Diethyl D-(+)-Malate Diethyl L-(-)-Malate Diethyl D-(-)-Tartrate Diethyl L-(+)-Tartrate Diisopropyl D-(-)-Tartrate Diisopropyl L-(+)-Tartrate Dimethyl (+)-2,3-O-Isopropylidene-D-tartrate Dimethyl (-)-2,3-O-Isopropylidene-L-tartrate Dimethyl D-(+)-Malate Dimethyl L-(-)-Malate Dimethyl (S)-(+)-2-Methylglutarate Dimethyl (R)-(+)-Methylsuccinate Dimethyl (S)-(-)-Methylsuccinate Dimethyl (2R,3R)-2,3-O-(1-Phenylethylidene)-L-tartrate Dimethyl D-(-)-Tartrate Dimethyl L-(+)-Tartrate Ethyl (R)-1-(tert-Butoxycarbonyl)-3-piperidinecarboxylate Ethyl N-(tert-Butoxycarbonyl)-D-pyroglutamate

1g 5g 5g 5g 5g 1g 1g 1g 5g 5g 1g 200mg

OH

OH

R0063

OH

O

T2902 H

HO O

O

N OH

162

O

M2350

O

OCH3

L0163

CH3

OCH3

OCH3 CH3

CH3 Cl

L0136 O

O

O OCH3

Cl

H0956

O

CH3

OCH3 CH3

H0703

CH3O C

C1634 O

Br

OCH3 CH3

D2562

C1633 O

O OCH3

O

Materials Chemistry

B2140

OH

O O CCl3

Unit Size

Availability or specification of the listed products are subject to change without prior notice.

25g 5g 5g 25g 25g 25g 25g 5g 5g 5g

5g

1g

5g 25g 25g 25g 25g 5g 5g 25g 25g 5g 1g 25g 1g 500g 25g 25g 250g 500g 250g 500g 5g 25g 25g 25g 5g 5g 5g 5g 25g 25g 5g 5g

Chiral Building Blocks

Ethyl (R)-(+)-1-Ethyl-2-pyrrolidinecarboxylate Ethyl (S)-(-)-1-Ethyl-2-pyrrolidinecarboxylate Ethyl (R)-2-Hydroxy-4-phenylbutyrate Ethyl L-(-)-Lactate Ethyl D-(-)-Mandelate Ethyl L-(+)-Mandelate Ethyl (R)-(-)-3-Piperidinecarboxylate Ethyl (S)-(+)-3-Piperidinecarboxylate Ethyl L-(-)-O-Tosyllactate (S)-(+)-γ-Hydroxymethyl-γ-butyrolactone L-(-)-Lactide Methyl (R)-(+)-3-(Acetylthio)-2-methylpropionate Methyl (R)-(+)-3-Bromoisobutyrate Methyl (S)-(-)-3-Bromoisobutyrate Methyl (R)-(+)-2-Chloropropionate Methyl (S)-(-)-2-Chloropropionate Methyl (R)-(+)-2,2-Dimethyl-1,3-dioxolane-4-carboxylate Methyl (R)-(-)-3-Hydroxyisobutyrate Methyl (R)-(+)-2-(4-Hydroxyphenoxy)propionate Methyl D-(+)-Lactate Methyl L-(-)-Lactate Methyl D-(-)-Mandelate Methyl L-(+)-Mandelate Methyl D-3-Phenyllactate Methyl L-Pyroglutamate D-(-)-Pantolactone D-(+)-Ribono-1,4-lactone (2R,5S)-2-Trichloromethyl-3-oxa-1-azabicyclo[3.3.0]octan-4-one

Unit Size

A1169

B3756

CH3

O N

NH2 NH2

A1124 O NH C CH3

(CH3)3C

Si O H 3C CH3

O

H

CH3

CH3 C

Si

CH3 CH3

O

CH3 CO2H

O

O

E0468

O

O

O

O

D3676

D4347

CH2CH3

O

OH

N H

C NH2

C NH

O

CH3

H0867

L0167 O

O N

CH3

O

CH3

CH2

N H

H1241

O C NH2

OH

O

E0452

N

CH2

O

NH O

H N

O

OC(CH3)3

N H

O

CH3 O

NH

B4026

CH3

D1539

H N

H N

H

C NH2

CH2CH3

O O C CH3

CH3 CH3

CH3

C NH C CH3 NH

H H

O

H

C2699

CH3

B1776

C NH2

O

C2678

5g 25g 1g 1g 1g 25g 25g 1g

N H

C OC(CH3)3

. HCl

5g 5g

O

B3410

O

1g 1g

NH C CH3 N H

5g 5g 5g 500g 25g 25g 25g 25g 25g 5g 250g 5mL 5g 5g 5g 5g 25g 25g 25g 25g 500g 5g 5g 5g 100g 500g 5g 1g

25g 5g 5g 5g 5g 1g 1g 25g

A1170

Amides

A2252

1g 1g

Materials Chemistry

Product Name

E0469 E0450 H0904 L0162 M1344 M1273 N0655 N0679 T1241 H0958 L0115 A1383 B2139 B2140 C1633 C1634 D2562 H0703 H0956 L0136 L0163 M1349 M1350 M2350 M2198 P0011 R0063 T2902

Synthetic Organic Chemistry

Product No.

HOCH2

N H

O

HOCH2

N H

O

CH3

NH2 OH

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

163

Chiral Building Blocks

Synthetic Organic Chemistry

M2198

P2083

N H

O

P1382

T1702

O

OCH3

N H

O

N H

OH

H N

O

C NH2

T1369

C NH2

O

O

NH C CF3 OH

O

OH

. HCl

N H

T1366 O NH C CF3

. HCl

Materials Chemistry

N H

Product No.

Product Name

A1169 A1170 A1124 A2252 B3756 B3410 B1776 B4026 C2678 C2699 D1539 D3676 D4347 E0468 E0452 H1241 H0867 L0167 M2198 P2083 P1382 T1702 T1369 T1366

(3R)-(+)-3-Acetamidopyrrolidine (3S)-(-)-3-Acetamidopyrrolidine (3R,4R)-4-Acetoxy-3-[(R)-(tert-butyldimethylsilyloxy)ethyl]-2-azetidinone (S)-2-Aminobutyramide Hydrochloride N-(tert-Butoxycarbonyl)-L-prolinamide (S)-N-tert-Butyldecahydroisoquinoline-3-carboxamide (3S,4S)-3-[(R)-1-(tert-Butyldimethylsilyloxy)ethyl]-4-[(R)-1-carboxyethyl]-2-azetidinone tert-Butyl L-Pyroglutamate (R)-β-(Carbobenzoxyamino)-γ-butyrolactone N-Carbobenzoxy-L-homoserine Lactone (+)-N,N '-Diallyl-L-tartardiamide (S)-(+)-2,2-Dimethylcyclopropanecarboxamide (S)-N-(2,6-Dimethylphenyl)piperidine-2-carboxamide (R)-(+)-1-Ethyl-2-pyrrolidinecarboxamide (S)-(-)-1-Ethyl-2-pyrrolidinecarboxamide (R)-5-(Hydroxymethyl)-2-pyrrolidinone (S)-5-(Hydroxymethyl)-2-pyrrolidinone (R)-(+)-Lactamide Methyl L-Pyroglutamate D-Prolinamide L-Prolinamide (2R,3R)-Tartranilic Acid (3R)-(+)-3-(Trifluoroacetamido)pyrrolidine Hydrochloride (3S)-(-)-3-(Trifluoroacetamido)pyrrolidine Hydrochloride

Unit Size

I0468

I0334

Isocyanates

CH3

5g 5g 1g 5g 1g 1g 5g 1g 1g 1g 1g 5g 25g 1g 5g 1g 1g 1g

I0335 CH3

O

5g 5g 25g 25g 5g 25g 1g 5g 1g 5g 25g 25g 5g 5g 5g 5g 5g 25g 100g 5g 25g 5g 25g 25g

CH3

NCO

NCO

O

O

O

CH3

NCO

I0473

I0466 O

tBuO

164

CH3 O OCH3

NCO

I0471

CH3

I0472

CH3

OCH3 NCO

O

O

CH3 O OCH3

NCO

I0467

CH3

OCH3

OCH3 CH3

NCO

Availability or specification of the listed products are subject to change without prior notice.

NCO

Chiral Building Blocks

I0465

I0336 NCO

CH3

Synthetic Organic Chemistry

CH3

O CH3

I0398 NCO

OCH3 NCO

Product Name

I0468 I0334 I0335 I0473 I0466 I0471 I0467 I0472 I0465 I0336 I0398

Diethyl (S)-(-)-2-Isocyanatoglutarate (R)-(+)-α-Methylbenzyl Isocyanate (S)-(-)-α-Methylbenzyl Isocyanate Methyl (S)-(+)-2-Isocyanato-3-tert-butoxypropionate Methyl (S)-(-)-2-Isocyanato-3-methylbutyrate Methyl (2S,3S)-2-Isocyanato-3-methylvalerate Methyl (S)-(-)-2-Isocyanato-4-methylvalerate Methyl (S)-2-Isocyanato-3-phenylpropionate Methyl (S)-(-)-2-Isocyanatopropionate (R)-(-)-1-(1-Naphthyl)ethyl Isocyanate (S)-(+)-1-(1-Naphthyl)ethyl Isocyanate

Unit Size 1g

5g 1g 1g 1g

A0973

CH3

5g 25g 5g 1g 5g 5g 25g 5g 5g 5g 5g

1g

A0972

Amino Alcohols

1g 5g 1g

A2503

CH3

OH

Materials Chemistry

Product No.

OH

NH2

CH3

NH2

CH3

OH

CH3 NH2

A1230

A1231

A2306

A1623

A1624

NH2

NH2

OH OH

OH

A2307

OH

NH2

A2533

OH

NH2

A2504

NH2

A1017

A2002 OH

CH3 OH NH2

D2128

D2129

CH2OH

CH3

Bu NHCH2

NH2

L0160

OH NH

OH

OH NH2

CH3

N Bu

L0236

(CH3)3C

CH3

CH3 Bu

N Bu

I0476

I0462

CH3

OH

OH CH3

NH2

OH NH2

OH

L0137

CH3

OH NH2

NH2

O2N

NH2

B1119

CH3

OH

OH

CH3

CH3 NH2

A1085

CH3

CH3

OH

M0929

CH3

OH CH3

NH2

CH3S

OH NH2

CH3

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

165

Chiral Building Blocks

Synthetic Organic Chemistry

N0608

N0631 CH3

HO

P1028

P1201

CH3

NH2

HO

NH2

OH

OH

OH

NH2

NH2

NH2

P1294

P1274

P1087

T1755

T1537

CH2OH OH

N H

NH2

Materials Chemistry

P1289

V0077

N H

CH2OH

OH

NH

NH2

N H

V0058 CH3

CH3 CH3

OH

CH3

OH NH2

NH2

166

CH2OH

Product No.

Product Name

A0972 A0973 A2503 A1230 A1231 A2306 A1623 A1624 A2307 A2533 A2504 A1017 A2002 A1085 B1119 D2128 D2129 I0462 I0476 L0160 L0236 L0137 M0929 N0608 N0631 P1289 P1028 P1201 P1294 P1274 P1087 T1755 T1537 V0077 V0058

(R)-(-)-2-Amino-1-butanol (S)-(+)-2-Amino-1-butanol (S)-(-)-2-Amino-3,3-dimethyl-1,1-diphenyl-1-butanol (1R,2S)-(-)-2-Amino-1,2-diphenylethanol (1S,2R)-(+)-2-Amino-1,2-diphenylethanol (1R,2R)-(-)-1-Amino-2-indanol (1R,2S)-(+)-1-Amino-2-indanol (1S,2R)-(-)-1-Amino-2-indanol (1S,2S)-(+)-1-Amino-2-indanol (R)-(+)-2-Amino-3-methyl-1,1-diphenyl-1-butanol (S)-(-)-2-Amino-3-methyl-1,1-diphenyl-1-butanol D-(-)-threo-2-Amino-1-(4-nitrophenyl)-1,3-propanediol (R)-(-)-2-Amino-1-propanol (S)-(+)-2-Amino-1-propanol (+)-cis-2-Benzylaminocyclohexanemethanol (1R,2S)-2-(Dibutylamino)-1-phenyl-1-propanol (1S,2R)-2-(Dibutylamino)-1-phenyl-1-propanol L-Isoleucinol (R)-2-Isopropylamino-2-phenylethanol L-tert-Leucinol D-(-)-Leucinol L-(+)-Leucinol L-(-)-Methioninol (1R,2S)-(-)-Norephedrine (1S,2R)-(+)-Norephedrine D-Phenylalaninol L-Phenylalaninol (R)-(-)-2-Phenylglycinol (S)-(+)-2-Phenylglycinol D-Prolinol L-Prolinol (S)-1,2,3,4-Tetrahydroisoquinoline-3-methanol L-(-)-Tryptophanol D-Valinol L-Valinol

Unit Size

Availability or specification of the listed products are subject to change without prior notice.

1mL 1g 1g 1g 1g 1g 1g 1g 1g 25g 5mL 1mL 5mL 1g 1g 1g 1g 5g 1g 1g 5mL 100mg

1g

5g 5g 5g 5g 5g 5g

1g 5g

5mL 5mL 5g 5g 5g 5g 5g 5g 5g 1g 5g 500g 25mL 25mL 5g 5g 5g 5g 25g 5g 5g 25mL 1g 25g 25g 25g 25g 25g 25g 25g 25g 1g 1g 5g 25g

Chiral Building Blocks

B1953

B2174

-Protected Amino Alcohols

OH

OH OC(CH3)3

HN

N

B3662

B4283

HO N

HN

C OC(CH3)3

HN O

B3077

C2629

C1609

CH3 OC(CH3)3

HN

OH

N O

O

OC(CH3)3

HN O

B3076

OH

OH

OC(CH3)3

OC(CH3)3

OH

N O

OH HN

OC(CH3)3

Materials Chemistry

B3272

OH

OC(CH3)3 O

O

O

B3270

OH HN

OC(CH3)3

OC(CH3)3 O

B2604

OH

CH2OH

N

O

B1966

CH3S

OH

OC(CH3)3

O

Synthetic Organic Chemistry

CH3

B2123

OH HN

O

O O

O

C1610

OH HN

O O

Product No.

Product Name

B1953 B2174 B2123 B3662 B4283 B1966 B2604 B3270 B3272 B3076 B3077 C2629 C1609 C1610

N-(tert-Butoxycarbonyl)-L-alaninol (R)-1-(tert-Butoxycarbonyl)-2-azetidinemethanol (S)-1-(tert-Butoxycarbonyl)-2-azetidinemethanol (2S,4R)-1-(tert-Butoxycarbonyl)-4-hydroxy-2-(hydroxymethyl)pyrrolidine N-(tert-Butoxycarbonyl)-L-methioninol N-(tert-Butoxycarbonyl)-D-phenylalaninol N-(tert-Butoxycarbonyl)-L-phenylalaninol N-(tert-Butoxycarbonyl)-D-2-phenylglycinol N-(tert-Butoxycarbonyl)-L-2-phenylglycinol N-(tert-Butoxycarbonyl)-D-prolinol N-(tert-Butoxycarbonyl)-L-prolinol N-Carbobenzoxy-L-alaninol N-Carbobenzoxy-D-phenylalaninol N-Carbobenzoxy-L-phenylalaninol

Unit Size

A2049

1g 100mg 100mg 1g 1g 1g 1g 1g 1g 5g 1g 1g 1g

A1979

5g 1g 1g 5g 5g 5g 5g 5g 5g 5g 25g 5g 5g 5g

A1980

OH

Simple Alcohols

H2N

N

OH

H2N

OH

OH

C CH3

OH

O

A0974

A0975

A1839

A2635

H1200 HO

CH3

H2N OH

CH3

H2N OH

HO

OH

HO

N

relative

O

CH2OH

OH O

CH2OH

CH2

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

167

Chiral Building Blocks

Synthetic Organic Chemistry

B2899

B2900

O

B2901

B4117

B1532

OH

B4118

B1533

B4131 OH

OH

OH

CH3

C O C CH3

C O C CH3 O

CH3

CH3

CH3

CH3

CH3

OH

B2910

HC

OH

C

OH

C2423 OH

Cl

N

N

C OCH2

C OCH2

O

O

D4010

OH

OH

O

CH3

Cl

CH3

OH HS

SH OH

C1474

OH

O

N OH

C1717

OH Cl

CH3 S

O OH

C1733

Cl

D1589

OH O

O

OH

O

Cl

D2240

O

OH

CN OH

D2239

E0455

CH3

C2424

OH

OH

C

OH

OH

C2763

OH

M0967

HC

CH3

CH3

C2453

OH

B0925

B2909

(CH3)3CHN

CH3

O

O

OH

OH

B1987

N

C2585

168

OH

CH3

CH3

OH

OH

CH3

Cl

CH3

OH

B3055 OH

HO

HO

OH

OH

B0926

OH

B3054

N

OH

CF3

B1161

OH

B2404

OH

OH

CF3

B1160

CH3

HO

CH3

CH3

CH2

OH

B3137 OH

N

CH2

OH OH

B1343

N

B1159

OH

CH3

CH3

O

B4119

CH3

OH OH

OH

OH O

O

O

OH

OH

OH

Materials Chemistry

OH

O

OH

OH

B2142

B2141

OH

O

OH

B2902

O

H1029

OH O

CH3

NC

O

OH O

CH3

Availability or specification of the listed products are subject to change without prior notice.

CH3

O O

CH3

Chiral Building Blocks

H0975

H1032

O

H0939

CH3

CH3

CH3

H0951

OH

OH

O

CH3

H0950 OH

OH

CH3

CH3

OH

O

OH

H1384

H0887

O

O

H1368

O

OH

HO

O

M1788

M1790

CH3O

OH

N H

CH3

H0705

OCH3

H0704

H N

S

OH

OH

OH

M1483

M2157

CH3

OH O

OH

O

O

M2166

CH3O O

O

OH

O

M1937

Cl

OCH3

N0784

OH

O OCH3

CH3

N0785

M1938

OCH3

CH3

OH

CH3

CH3

OH

O

O0293

OH

N

N

CH3

CH3

O0145

O0144

OH

OH

CH3

CH3

CH3

CH3

OH

O0235

P1411

CH3

C

CH

CH3 OH

OH

T1490

P1412

CH3

P0744

CH3

T1491

OH

P1150

OH

P0796

OH CH3

OH

CH3

CH3

P0795 HO

OH

CH3

OH

OH

P1930 CH3

CH3

OH CH3

P1151 HO

OH CH3

P0743

CH3 OH

OH

CH3

OH

OH OH

Materials Chemistry

T1716

OH

O CH3

O

H1332

HO

HO HO

Synthetic Organic Chemistry

OH

H0969

OH

P1931 OH

CH3

P1417

P1780

OH OH

OH

CH3 CH3

CH3

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

169

Chiral Building Blocks

Synthetic Organic Chemistry

P1152

P1129

CH3

OH

P1608

OH

OH

OH OH

S0038

P1140

OH

CH3

OH

P1667

N H

T2359

N H

T2360

. HCl

N H

T1499

T1482

O C OH

HO

OH

OH

OH

OH

OH

OH

OH

Materials Chemistry

OH

170

Product No.

Product Name

A2049 A1979 A1980 A0974 A0975 A1839 A2635 H1200 B2899 B2900 B2901 B2902 B2141 B2142 B4117 B1532 B1533 B4131 B4118 B4119 B1159 B1160 B1161 B1343 B3137 B2404 B0926 B0925 B3054 B3055 B1987 B2909 B2910 C2585 C2453 C2763 C2423 C2424 M0967 D2239 D2240 D4010 D1589 E0455 C1733 C1717 C1474 H1029 H0975 H1032

(R)-1-Acetyl-3-pyrrolidinol (R)-3-Amino-1,2-propanediol (S)-3-Amino-1,2-propanediol (R)-(-)-1-Amino-2-propanol (S)-(+)-1-Amino-2-propanol 1,4-Anhydroerythritol 1,4-Anhydro-D-xylitol (3R,4R)-1-Benzyl-4-hydroxy-3-pyrrolidinemethanol (R)-4-Benzyloxy-1,2-butanediol (S)-4-Benzyloxy-1,2-butanediol (R)-4-Benzyloxy-1,3-butanediol (S)-4-Benzyloxy-1,3-butanediol (R)-(+)-3-Benzyloxy-1,2-propanediol (S)-(-)-3-Benzyloxy-1,2-propanediol (S)-(+)-1-Benzyloxy-2-propanol (R)-1-Benzyl-3-pyrrolidinol (S)-1-Benzyl-3-pyrrolidinol (R)-1-[3,5-Bis(trifluoromethyl)phenyl]ethanol (R)-1,2-Butanediol (S)-1,2-Butanediol (R)-(-)-1,3-Butanediol (S)-(+)-1,3-Butanediol (R,R)-(-)-2,3-Butanediol (S,S)-(+)-2,3-Butanediol (R)-1,2,4-Butanetriol (S)-1,2,4-Butanetriol (R)-(-)-2-Butanol (S)-(+)-2-Butanol (R)-1-(tert-Butoxycarbonyl)-3-pyrrolidinol (S)-1-(tert-Butoxycarbonyl)-3-pyrrolidinol (S)-(-)-3-tert-Butylamino-1,2-propanediol (R)-(+)-3-Butyn-2-ol (S)-(-)-3-Butyn-2-ol (R)-1-Carbobenzoxy-3-pyrrolidinol (S)-1-Carbobenzoxy-3-pyrrolidinol (R)-(+)-4-Chloro-3-hydroxybutyronitrile (R)-(+)-3-Chloro-1-phenyl-1-propanol (S)-(-)-3-Chloro-1-phenyl-1-propanol (R)-(-)-3-Chloro-1,2-propanediol (+)-1,4-Di-O-benzyl-D-threitol (-)-1,4-Di-O-benzyl-L-threitol (S)-3-(Dimethylamino)-1-(2-thienyl)-1-propanol L-Dithiothreitol D-Erythronolactone Ethyl (R)-4-Chloro-3-hydroxybutyrate Ethyl (S)-4-Chloro-3-hydroxybutyrate Ethyl (R)-(-)-4-Cyano-3-hydroxybutyrate Ethyl (R)-(-)-3-Hydroxybutyrate Ethyl (S)-(+)-3-Hydroxybutyrate (2R,5R)-2,5-Hexanediol

Unit Size

Availability or specification of the listed products are subject to change without prior notice.

1g

1g 1g 5g 1g 20mg 200mg 200mg

100mg 100mg 1g 1g 5g 5g 1g 1g 1g 1g 1g 100mg 1g 5g 1mL 1mL 1g 1g 1g 1g 1g 1g

10g

1g

1g

1g 1g 5g 5g 5g 5g 1g 5g

1g 5g 5g 25g 5g 5g 100mg 200mg 1g 1g 1g 1g 1g 1g 5g 5g 25g 25g 5g 5g 5g 5g 5g 1g 5g 25g 5mL 5mL 5g 5g 5g 5g 1g 5g 5g 5g 1g 1g 25g 1g 1g 5g 5g 25g 25g 25g 25g 5g 25g 1g

Chiral Building Blocks

(2S,5S)-2,5-Hexanediol (R)-(+)-α-Hydroxy-γ-butyrolactone (S)-(-)-α-Hydroxy-γ-butyrolactone (S)-3-Hydroxy-γ-butyrolactone 4-(cis-4-Hydroxycyclohexyl)phenol (S)-(+)-3-Hydroxy-2,2-dimethylcyclohexanone (S)-(-)-4-Hydroxy-2-pyrrolidone (R)-3-Hydroxytetrahydrofuran (S)-3-Hydroxytetrahydrofuran (R)-4-(4-Methoxybenzyloxy)-1,2-butanediol (S)-4-(4-Methoxybenzyloxy)-1,3-butanediol (R)-(-)-1-Methoxy-2-propanol (S)-3-(Methylamino)-1-(2-thienyl)-1-propanol Methyl (R)-4-Chloro-3-hydroxybutyrate Methyl (R)-(-)-3-Hydroxybutyrate Methyl (S)-(+)-3-Hydroxybutyrate (R)-1-Methyl-3-pyrrolidinol (S)-1-Methyl-3-pyrrolidinol (R)-(+)-1-(2-Naphthyl)ethanol (S)-(-)-1-(2-Naphthyl)ethanol (3R,6R)-3,6-Octanediol (R)-(-)-2-Octanol (S)-(+)-2-Octanol (S)-1-Octyn-3-ol (2R,4R)-(-)-2,4-Pentanediol (2S,4S)-(+)-2,4-Pentanediol (R)-(-)-2-Pentanol (S)-(+)-2-Pentanol (1R,2S)-(-)-trans-2-Phenyl-1-cyclohexanol (1S,2R)-(+)-trans-2-Phenyl-1-cyclohexanol (R)-(-)-1-Phenylethane-1,2-diol (S)-(+)-1-Phenylethane-1,2-diol (R)-(+)-1-Phenylethyl Alcohol (S)-(-)-1-Phenylethyl Alcohol (R)-(+)-1-Phenyl-1-propanol (S)-(-)-1-Phenyl-1-propanol (R)-1-Phenyl-2-propanol (S)-1-Phenyl-2-propanol (R)-(-)-1,2-Propanediol (S)-(+)-1,2-Propanediol (R)-3-Pyrrolidinol (S)-3-Pyrrolidinol (R)-(-)-3-Pyrrolidinol Hydrochloride Shikimic Acid (R)-(-)-1,2,3,4-Tetrahydro-1-naphthol (S)-(+)-1,2,3,4-Tetrahydro-1-naphthol (R)-(+)-1,1,2-Triphenyl-1,2-ethanediol (S)-(-)-1,1,2-Triphenyl-1,2-ethanediol

Unit Size 1g 100mg 1g

1g 1g

5g 5g 10mL 5mL 1g 1g

5mL 5mL 1g

1mL 1mL 100mg 100mg 1g 5g 1g 1g 5g 1g 5g

5g 1g 5g 5g 100mg 1g 100mg 100mg 1g 1g

A2335

A2512

5g 1g 100mg 5g 1g 100mg 1g 5g 5g 500mg 500mg 25g 25g 5g 25mL 25mL 5g 5g 1g 1g 500mg 25mL 25mL 5g 1g 1g 5mL 5mL 1g 1g 25g 5g 25g 25g 1g 1g 1mL 1mL 25g 5g 5g 25g 25g 5g 1g 1g 5g 1g

Materials Chemistry

Product Name

H0969 H0950 H0951 H0939 H1384 H0887 H1368 H1332 T1716 M1788 M1790 M2166 M2157 M1483 H0705 H0704 M1937 M1938 N0784 N0785 O0293 O0145 O0144 O0235 P1411 P1412 P0744 P0743 T1490 T1491 P1150 P1151 P0795 P0796 P1930 P1931 P1417 P1780 P1152 P1129 P1608 P1667 P1140 S0038 T2359 T2360 T1499 T1482

Synthetic Organic Chemistry

Product No.

A1445

NH2 NH2

Amines

N

CH3

C O C CH3 O

A2323

A2324 NH2

. HCl

N

N

C OCH2

C OCH2

O

O

. HCl

O

O

. HCl

O

CH3

A2286 NH2

O

NH2

. HCl

A2473

A2533

O C OH

N

NH2

O

CH3

CH2NH2

C OC(CH3)3

OH

CH3 NH2

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

171

Chiral Building Blocks

Synthetic Organic Chemistry

A1342

A1301

A1167

A1168 NH2

N

CH2NH2

N

CH2CH3

CH2NH2

N H

CH2CH3

A1053

A1054

CH2NH2

. 2HCl

N H

B1580

B1581

A1174

B1932 NH C O C CH3 CH3

N

N

CH2

CH2

N CH2

B1583

NHCH2CH3

CH3

O

NH2

B1582

NHCH2CH3

N H

NH2

NH2

. 2HCl

NH2

N H

A1173

NH2 N H

Materials Chemistry

A2206

B2775

NHCH3

CH3

NHCH3 NH2 CH3

N

N

N

N

CH2

CH2

CH2

CH2

CH3 NH2

. xH3PO4

CH3

B2776

B3225

B2316

B2317

B3672

CH3 OCH3

NH2

CH3

NH2

CH3

NH2

CH3 NH2

CH3

CH3

CH3 NH2

CH3

CH3

CH3 NH2

. xH3PO4

NH2

CH3O

CH3

CH3

NH2

CH3

CH3

CH3

NH2

CH3

Br

CH3

B3674

B3538 NH2

CH3

B3539

B3591

O

O

C OH

C OH O

A1171

A1172 O NH

O NH

N

CH3 N H

B3483

B1995 O

CH3

NH C OC(CH3)3

O

CH3

C1575

C1447 O O

CH2O C HN O

O

CH3

B3478 NH2 N O

NH2

CH3

B2918

CH3

O NH C OC(CH3)3

CH3

C O C CH3

CH3

C2699

CH3

NH2

O

NH2

B2921

CH3

B2917

CH3 C O C HN

CH3 CH3

N H

C O C CH3 O

O

NH C O C CH3

N H

NH2

CH3

CH3 N H

172

NH C OC(CH3)3

C O C CH3

CH3 CH3

B2920

CH3

C O C CH3

O

NH C O C CH3 O

NH C OC(CH3)3

Br

B3660

H N

CH3 NH2 O

C1448

C1541

NH2

NH2

NH2

NH2

O

O O

C1531 CH3

NH2

Availability or specification of the listed products are subject to change without prior notice.

CH3

NH2

Chiral Building Blocks

C1189

D4035

D4036 NH2

H2N

NH2

O

CH3

NH

O

D4258

N

N

CH2

CH2

D2149

CH3 CH3

CH3 N CH3

E0433

. 2HCl

D2460

N H

D2175

NH2

NH2

NHCH3

NHCH3

NHCH3

NHCH3

E0434

I0480

Materials Chemistry

D2176

CH3

CH3

. 2HCl

D2459

N CH3 N H

CH3

NH2

NH2

D2193

OH

N

D2828

Synthetic Organic Chemistry

H2N H 2N

D2827

CH3 NH2

NHCH2CH3

NH2

NH2

M1512 CH3

N H

NH2

M1511 NH2

M1108

M1746 NHCH3

CH3

CH2NH2

N H

OCH3

M1747

N0482

CH3

CH3 CH3

NH2

N H

OH HN

NHCH3

OCH3

CH3

N H

M1107 CH3

NHCH2CH3

N0481 CH3

CH2NH2

N0724 CH3

NH2

NH2

N0726 NH2

NH2

CH3

P0794

P0793 CH3

NH2

P1118 CH3

NH2

T2878 NH2

NH2

CH3

T1380

T2926

CH3

NH2

T1381 CH3

NH2

CH3

CH3

NH2

CH3

Product No.

Product Name

A2335 A2512 A1445 A2323 A2324 A2286

(S)-3-Amino-1-tert-butoxycarbonylpiperidine (R)-(+)-α-Amino-γ-butyrolactone Hydrochloride (S)-(-)-α-Amino-γ-butyrolactone Hydrochloride (R)-3-Amino-1-carbobenzoxypyrrolidine Hydrochloride (S)-3-Amino-1-carbobenzoxypyrrolidine Hydrochloride (1S,3R)-3-Aminocyclohexanecarboxylic Acid

Unit Size 1g 5g 1g 1g 5g 1g 5g 200mg 1g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

173

Materials Chemistry

Synthetic Organic Chemistry

Chiral Building Blocks

174

Product No.

Product Name

A2473 A2533 A1342 A1301 A2206 A1167 A1168 A1053 A1054 A1173 A1174 B1932 B1580 B1581 B1582 B1583 B2775 B2776 B3225 B2316 B2317 B3672 B3674 B3538 B3539 B3591 B3660 A1171 A1172 B2920 B2921 B3478 B3483 B1995 B2917 B2918 C2699 C1575 C1447 C1448 C1541 C1531 C1189 D4035 D4036 D2827 D2828 D4258 D2149 D2193 D2459 D2460 D2176 D2175 E0433 E0434 I0480 M1511 M1512 M1107 M1108 M1746 M1747 N0482 N0481 N0724 N0726 P0794

(S)-2-(Aminomethyl)-1-(tert-butoxycarbonyl)pyrrolidine (R)-(+)-2-Amino-3-methyl-1,1-diphenyl-1-butanol (R)-(+)-2-Aminomethyl-1-ethylpyrrolidine (S)-(-)-2-Aminomethyl-1-ethylpyrrolidine (S)-2-(Aminomethyl)pyrrolidine (3R)-(+)-3-Aminopyrrolidine (3S)-(-)-3-Aminopyrrolidine (3R)-(-)-3-Aminopyrrolidine Dihydrochloride (3S)-(+)-3-Aminopyrrolidine Dihydrochloride (3R)-(-)-1-Benzyl-3-aminopyrrolidine (3S)-(+)-1-Benzyl-3-aminopyrrolidine (3R)-(+)-1-Benzyl-3-(tert-butoxycarbonylamino)pyrrolidine (3R)-(-)-1-Benzyl-3-(ethylamino)pyrrolidine (3S)-(+)-1-Benzyl-3-(ethylamino)pyrrolidine (3R)-(-)-1-Benzyl-3-(methylamino)pyrrolidine (3S)-(+)-1-Benzyl-3-(methylamino)pyrrolidine (1R,2R)-1,2-Bis(3,5-dimethylphenyl)-1,2-ethylenediamine Phosphate (1S,2S)-1,2-Bis(3,5-dimethylphenyl)-1,2-ethylenediamine Phosphate (1R,2R)-1,2-Bis(4-methoxyphenyl)ethylenediamine (1R,2R)-1,2-Bis(2,4,6-trimethylphenyl)ethylenediamine (1S,2S)-1,2-Bis(2,4,6-trimethylphenyl)ethylenediamine (R)-(+)-1-(4-Bromophenyl)ethylamine (S)-(-)-1-(4-Bromophenyl)ethylamine (1R,3S)-3-(tert-Butoxycarbonylamino)cyclohexanecarboxylic Acid (1S,3R)-3-(tert-Butoxycarbonylamino)cyclohexanecarboxylic Acid (R)-3-(tert-Butoxycarbonylamino)piperidine (S)-3-(tert-Butoxycarbonylamino)piperidine (3R)-(+)-3-(tert-Butoxycarbonylamino)pyrrolidine (3S)-(-)-3-(tert-Butoxycarbonylamino)pyrrolidine (3R)-(+)-1-(tert-Butoxycarbonyl)-3-aminopyrrolidine (3S)-(-)-1-(tert-Butoxycarbonyl)-3-aminopyrrolidine (1R,2S)-N1-(tert-Butoxycarbonyl)-1,2-cyclohexanediamine (1S,2R)-N1-(tert-Butoxycarbonyl)-1,2-cyclohexanediamine N-(tert-Butoxycarbonyl)-L-serine β-Lactone (R)-(-)-sec-Butylamine (S)-(+)-sec-Butylamine N-Carbobenzoxy-L-homoserine Lactone N-Carbobenzoxy-L-serine β-Lactone (1R,2R)-(-)-1,2-Cyclohexanediamine (1S,2S)-(+)-1,2-Cyclohexanediamine (R)-(-)-1-Cyclohexylethylamine (S)-(+)-1-Cyclohexylethylamine D-(+)-Cycloserine (3R,4R)-(-)-3,4-Diamino-1-benzylpyrrolidine (3S,4S)-(+)-3,4-Diamino-1-benzylpyrrolidine (R)-1,2-Diaminopropane Dihydrochloride (S)-1,2-Diaminopropane Dihydrochloride (S)-3-[1-(Dimethylamino)ethyl]phenol (3R)-(+)-3-(Dimethylamino)pyrrolidine (3S)-(-)-3-(Dimethylamino)pyrrolidine (1R,2R)-(-)-N,N '-Dimethylcyclohexane-1,2-diamine (1S,2S)-(+)-N,N '-Dimethylcyclohexane-1,2-diamine (1R,2R)-(+)-1,2-Diphenylethylenediamine (1S,2S)-(-)-1,2-Diphenylethylenediamine (3R)-(+)-3-(Ethylamino)pyrrolidine (3S)-(-)-3-(Ethylamino)pyrrolidine (S)-2-Isopropylamino-3-methyl-1-butanol (R)-(+)-1-(4-Methoxyphenyl)ethylamine (S)-(-)-1-(4-Methoxyphenyl)ethylamine (3R)-(+)-3-(Methylamino)pyrrolidine (3S)-(-)-3-(Methylamino)pyrrolidine (R)-(+)-β-Methylphenethylamine (S)-(-)-β-Methylphenethylamine (R)-(+)-1-(1-Naphthyl)ethylamine (S)-(-)-1-(1-Naphthyl)ethylamine (R)-1-(2-Naphthyl)ethylamine (S)-1-(2-Naphthyl)ethylamine (R)-(+)-1-Phenylethylamine

Unit Size

Availability or specification of the listed products are subject to change without prior notice.

1g 1g 1g 1g 5g 200mg 1g 5g 25g 5g 25g 5g 25g 5g 25g 10g 25g 10g 25g 5g 5g 5g 5g 25g 5g 25g 100mg 100mg Price on request 100mg 500mg 100mg 500mg 1g 5g 5g 25g 1g 1g 1g 5g 1g 5g 5g 25g 5g 25g 1g 5g 1g 5g 1g 5g 1g 5g 1g 5g 100mg 1g 1g 1g 5g 1g 5g 25g 5g 25g 5g 25g 5g 25g 1g 5g 50mg 50mg 1g 1g 1g 5g 1g 5g 1g 5g 100mg 1g 100mg 1g 5g 1g 5g 1g 5g 1g 1g 5g 5g 25g 5g 25g 1g 5g 1g 5g 5g 25g 5g 25g 1g 5g 1g 5g 1g 5g 1g 5g 25mL 100mL 500mL

Chiral Building Blocks

Product Name

P0793 P1118 T2926 T2878 T1380 T1381

(S)-(-)-1-Phenylethylamine (S)-1-Phenyl-2-(p-tolyl)ethylamine (R)-(-)-1,2,3,4-Tetrahydro-1-naphthylamine (S)-(+)-1,2,3,4-Tetrahydro-1-naphthylamine (R)-(+)-1-(p-Tolyl)ethylamine (S)-(-)-1-(p-Tolyl)ethylamine

Unit Size 25mL 100mL 500mL 5g 25g 5g 25g 5g 25g 1mL 1mL 5mL

D2265

D3758 O

CH3

CH3

O

O

O

CH3

O

D2024

O O

CH3

O

CH3 CH3

I0507

CH3

COOH

O

CH3

.HO

CH3

CH3

O

CH3 O

I0376

O

O

O

CH2OH O

O

CH3

CH3

O

H3C

CH3

O

O

O

O

CH3

O O

OH

CH3 CH3

HO

O

CH3 CH3

I0489 O

OH

OH

HO

O

O

O

O

HO

CH2OH O

O

CH3

OH

HOH2C

O

CH3

CH2OH O

O

CH3

I0688

I0721

HOCH2

CH3 CH3

O

OH

O

O

H3C CH3

O

I0375

HOCH2

CH3

HO

O

OH

O

D2616

CH3

I0400

O

HO

O

O

CH3

2

I0454 O

O

OH

O

O

CH3

O

CH3

OH

O

OH O

CH3 O

CH3

D2447

CH3 CH3

O

OH

O

CH3 CH3

O

O

CH3

Materials Chemistry

D2191 O

O

CH3

O

O O

HO

CH3

D2555

CH3

Isopropylidene Sugars

D1949

Synthetic Organic Chemistry

Product No.

CH3

O

CH3 CH3

CH3

T2755 CH3

OH O

O O

O

O O

CH3

CH3 O

CH3

CH3

Product No.

Product Name

D2265 D3758 D2555 D1949 D2191 D2024 D2447 D2616 I0507 I0454 I0400 I0688 I0489 I0376 I0375 I0721 T2755

1,2:5,6-Di-O-isopropylidene-α-D-allofuranose 2,3:4,5-Di-O-isopropylidene-β-D-fructopyranose 1,2:3,4-Di-O-isopropylidene-α-D-galactopyranose 1,2:5,6-Di-O-isopropylidene-α-D-glucofuranose (-)-2,3:4,6-Di-O-isopropylidene-2-keto-L-gulonic Acid Monohydrate 1,2:5,6-Di-O-isopropylidene-D-mannitol 2,3:5,6-Di-O-isopropylidene-D-mannofuranose 1,2:3,5-Di-O-isopropylidene-α-D-xylofuranose (+)-5,6-O-Isopropylidene-L-ascorbic Acid 2,3-O-Isopropylidene-D-erythronolactone 1,2-O-Isopropylidene-α-D-glucofuranose 1,2-O-Isopropylidene-α-D-glucurono-6,3-lactone 3,4-O-Isopropylidene-D-mannitol (+)-2,3-O-Isopropylidene-L-threitol (-)-2,3-O-Isopropylidene-D-threitol 1,2-O-Isopropylidene-α-D-xylofuranose Topiramate

CH3

O

OSO2NH2

Unit Size 1g 5g 5g 10g 5g

5g

1g 1g 1g 5g 1g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

5g 25g 25g 25g 5g 25g 5g 5g 25g 1g 25g 1g 5g 5g 5g 25g 5g

175

Chiral Building Blocks

Synthetic Organic Chemistry

B2136

CH2OCH2

Protected 1,2/1,3-Diols

O O

B3642

B3690

B3702 CH3 CH3

CH2OCH2

O

CH3 CH3

B4214

O

O

CH3 CH3

C2265

O

O

H2N

OC(CH3)3

C1796

O

O

CH3

CH2 C O C CH3

NCCH2

N H CH3

CH3

O

CH3

O

CH3 CH3 N

O

CH3

F

O

CH3

O

(CH3)3CO

Materials Chemistry

B2137

D1705

O

O

HO

CH3 CH3

D2549

O

O CH3

HOCH2CH2

O

CH(CH3)2

P1485

O

CH3

O

O

O

CH3

CH3

O

CH3

S

HOCH2CH2

O O

O

CH3

CH(CH3)2 CH(CH3)2

O

M1456

CH3OCH2

CH3OCH2

O

CH3 CH3

HOCH2CH2

O

M1451

CH3 CH3

O

CH2O

O

O

O

O

O

P1486

CH3

CH3

O O

O

O O

O

Product No.

Product Name

B2136 B2137 B3702 B3642 B3690

(R)-4-Benzyloxymethyl-2,2-dimethyl-1,3-dioxolane (S)-4-Benzyloxymethyl-2,2-dimethyl-1,3-dioxolane tert-Butyl 2-[(4R,6R)-6-(2-Aminoethyl)-2,2-dimethyl-1,3-dioxan-4-yl]acetate tert-Butyl (4R,6R)-6-Cyanomethyl-2,2-dimethyl-1,3-dioxane-4-acetate tert-Butyl (4R,6R)-2-[6-[2-[2-(4-Fluorophenyl)-5-isopropyl-3-phenyl-4-(phenylcarbamoyl)pyrrol1-yl]ethyl]-2,2-dimethyl-1,3-dioxan-4-yl]acetate tert-Butyl (4R,6S)-6-(Hydroxymethyl)-2,2-dimethyl-1,3-dioxane-4-acetate (R)-4-Chloromethyl-2,2-dimethyl-1,3-dioxolane (S)-4-Chloromethyl-2,2-dimethyl-1,3-dioxolane (R)-(-)-2,2-Dimethyl-1,3-dioxolane-4-methanol 1g (S)-(+)-2,2-Dimethyl-1,3-dioxolane-4-methanol 1g (R)-(-)-2,2-Dimethyl-1,3-dioxolan-4-ylmethyl p-Toluenesulfonate (S)-(+)-2,2-Dimethyl-1,3-dioxolan-4-ylmethyl p-Toluenesulfonate (R)-4-(2-Hydroxyethyl)-2,2-diisopropyl-1,3-dioxolane (S)-4-(2-Hydroxyethyl)-2,2-diisopropyl-1,3-dioxolane (R)-4-(2-Hydroxyethyl)-2,2-dimethyl-1,3-dioxolane (S)-4-(2-Hydroxyethyl)-2,2-dimethyl-1,3-dioxolane (R)-(+)-4-(Methoxymethyl)-1,3-dioxolan-2-one (S)-(-)-4-(Methoxymethyl)-1,3-dioxolan-2-one (R)-Propylene Carbonate (S)-Propylene Carbonate

B4214 C2265 C1796 D1705 D1691 D2549 D2550 D4076 D4077 H1188 H1189 M1451 M1456 P1485 P1486

CH3

D4076 O

CH3

S

H1189

CH(CH3)2

O

176

O

H1188

HOCH2CH2

O

CH3

D2550 O

CH3 CH3

D4077

ClCH2 CH3

CH3

CH2OH O

O

OC(CH3)3

CH2O

O

O

CH3

D1691 CH2OH

O

ClCH2 O

Unit Size

Availability or specification of the listed products are subject to change without prior notice.

1g 1g 5g 5g 1g 5g 5g 1g

5g 5g 5g 5g

1g 1g 5g 5g 5g 25g 25g 5g 25g 25g 1g 5g 1g 1g 1g 1g 25g 25g 25g 25g

Chiral Building Blocks

B2238

B2239

E0893

Synthetic Organic Chemistry

H CH2OCH2

Glycidyl Compounds

B4111

B3832

CH2OCH2

O

O

B3833

E0581

O

E0533

CH3 CH3 CH2O Si

CH3

C CH3

CH3 CH3

O

O

G0364

CH2O C

O

G0281

O

O

NO2

CH2O

O

O

T1611

T1612

O

N CH2

O

N CH2

O

O

O

O

O CH3

CH2O S O

O

G0284

CH2O

NO2

O

O

G0328 O

G0409

CH2O S

O

O

G0327

O

G0411

CH2O S

O

O

CH2OCH3

(CH2)2CH3

O

NO2

CH2O S

G0410

O

G0287

CH2OCH3

G0280

CH2O C

(CH2)2CH3

O

G0286

O

G0283 O

CH2OH

O

O

O

G0282

CH2OH

CH2Cl

Materials Chemistry

G0363

CH2Cl

CH3

O

O OC(CH3)3

HN

CH3

CH2O S O

O

O

G0285

P1396

P0951

I0580 O

CH3 CH2O

C

CH2O

O

O

CH3

O

O

N

O

C

O

N

O

O

N O

I0581 O

N

O O

N

O

O

N O

Product No.

Product Name

B2238 B2239 E0893 B4111 B3832 B3833

Benzyl (R)-(-)-Glycidyl Ether Benzyl (S)-(+)-Glycidyl Ether (2S,3S)-3-(tert-Butoxycarbonylamino)-1,2-epoxy-4-phenylbutane tert-Butyldimethylsilyl (S)-Glycidyl Ether (R)-(+)-Butylene Oxide (S)-(-)-Butylene Oxide

Unit Size 1g 1g

5g 5g 5g 5mL 5mL

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

25g 25g 25g 5mL 25mL 25mL

177

Materials Chemistry

Synthetic Organic Chemistry

Chiral Building Blocks

Product No.

Product Name

E0581 E0533 G0363 G0364 G0282 G0283 G0280 G0281 G0286 G0287 G0411 G0409 G0410 G0327 G0328 T1611 T1612 G0284 G0285 P1396 P0951 I0580 I0581

(R)-Epichlorohydrin (S)-Epichlorohydrin (R)-(+)-Glycidol (S)-(-)-Glycidol (R)-Glycidyl Butyrate (S)-Glycidyl Butyrate (R)-Glycidyl Methyl Ether (S)-Glycidyl Methyl Ether (R)-Glycidyl 3-Nitrobenzenesulfonate (S)-Glycidyl 3-Nitrobenzenesulfonate (S)-Glycidyl 4-Nitrobenzenesulfonate (R)-Glycidyl Phenyl Ether (S)-Glycidyl Phenyl Ether (R)-N-Glycidylphthalimide (S)-N-Glycidylphthalimide (2R)-(-)-Glycidyl p-Toluenesulfonate (2S)-(+)-Glycidyl p-Toluenesulfonate (R)-Glycidyl Trityl Ether (S)-Glycidyl Trityl Ether (R)-(+)-Propylene Oxide (S)-(-)-Propylene Oxide (R,R,R)-Triglycidyl Isocyanurate (S,S,S)-Triglycidyl Isocyanurate

Unit Size 5g 5g 5g 5g 5g 5g 5g 5g 5g 5g

1mL

A1576

B2420

Others

B3694

CN

OH

O

N

CH3

B3693

B3299 H

O

H2N

N

C

H

B3695

1g 5g 5g 5g 5g 5g 5g 5mL 5mL

25g 25g 25g 25g 25g 25g 25g 25g 25g 25g 5g 1g 5g 25g 25g 25g 25g 25g 25g 25mL 25mL 1g 1g

CH2

B3696

B2779 CH3

N3CH2

O

OCH3 CH3

N3CH2

O

OCH3 CH3

HOCH2

O

OCH3 CH3

HOCH2

O

OCH3 CH3

N3CH2

O

CH3 OCH3

N3CH2

O

CH3 OCH3

HOCH2

O

CH3 OCH3

HOCH2

O

CH3 OCH3

O

Si C(CH3)3 CH3 CH3

BrHC

O

Si C(CH3)3 CH3

B1759

C1188

O

O

H C

N O

CH3

C O C CH3 CH3

CH3

Cl

CH3

O

OSO2CF3

M1234

OH

OH

O

CH

CH3

CH3 C NH

CH3

CH

Ph

O

M0966

CH3 OH

CH3

C OH

M0964

CH3 CH3

N

O OH H N

CH3

M0965

CH3

OCH3

M0824

N

OCH3

CH3

N

O

O

CH3OCH2

M0170

O

M1622

O H H

CH3O

CH3

M0803

CH3O H H O O

CH3

CH3 O

O

D3257

N

N

CH3

I0390

HO

D3259

CN CH3

CH3

E0879

178

C1363

OH CH3

Availability or specification of the listed products are subject to change without prior notice.

CH3

OH CH3

Chiral Building Blocks

M0963

M2091

M1424

OH

P1504

N H

P1509

O

H N CH3

N H

P1500 O

CH3

T2551

T2552

T2636 H3C

O O

Synthetic Organic Chemistry

H N

CH3 CH3

P1499

CH2NH2

O

O

CH2NH2

O

O

Materials Chemistry

V0117

CH2 CH3

CH3

CH3

Product No.

Product Name

A1576 B2420 B3299 B3693 B3694 B3695 B3696 B2779 B1759 C1188 C1363 D3259 D3257 E0879 I0390 M0803 M1622 M0824 M1234 M0170 M0965 M0964 M0966 M0963 M2091 M1424 P1499 P1500 P1504 P1509 T2551 T2552 T2636 V0117

(R)-4-Amino-2-methyl-1-butanol (4aS,8aR)-2-Benzoyloctahydro-6(2H)-isoquinolinone (R)-1-Benzyl-3-pyrrolidinecarbonitrile (2R,3R,5S,6S)-5,6-Bis(azidomethyl)-2,3-dimethoxy-2,3-dimethyl-1,4-dioxane (2S,3S,5R,6R)-5,6-Bis(azidomethyl)-2,3-dimethoxy-2,3-dimethyl-1,4-dioxane (2R,3R,5S,6S)-5,6-Bis(hydroxymethyl)-2,3-dimethoxy-2,3-dimethyl-1,4-dioxane (2S,3S,5R,6R)-5,6-Bis(hydroxymethyl)-2,3-dimethoxy-2,3-dimethyl-1,4-dioxane (1R,3R)-5-(Bromomethylene)-1,3-bis(tert-butyldimethylsilyloxy)cyclohexane (S)-(-)-3-(tert-Butoxycarbonyl)-4-formyl-2,2-dimethyl-1,3-oxazolidine (S)-(+)-1-Chloro-2-methylbutane (-)-2-Cyano-6-phenyloxazolopiperidine (5S)-5,6-Dihydro-6,6-dimethyl-5-phenyl-2H-1,4-oxazin-2-one (2S)-2,5-Dihydro-2-isopropyl-3,6-dimethoxypyrazine Ethyl (R)-4-Phenyl-2-(trifluoromethanesulfonyloxy)butyrate Isosorbide Dimethyl Ether (4S,5S)-(-)-4-Methoxymethyl-2-methyl-5-phenyl-2-oxazoline (R)-(+)-N-(α-Methylbenzyl)phthalamic Acid (S)-(-)-N-(α-Methylbenzyl)phthalamic Acid (S)-(-)-2-Methyl-1,4-butanediol (S)-(-)-2-Methyl-1-butanol (S)-(+)-5-Methyl-1-heptanol (S)-(+)-4-Methyl-1-hexanol (S)-(+)-6-Methyl-1-octanol (S)-(+)-3-Methyl-1-pentanol (R)-(-)-2-Methylpiperazine (S)-(+)-2-Methylpiperazine (R)-3-Phenylcyclohexanone (S)-3-Phenylcyclohexanone (R)-3-Phenylcyclopentanone (S)-3-Phenylcyclopentanone (R)-(-)-Tetrahydrofurfurylamine (S)-(+)-Tetrahydrofurfurylamine (R)-(-)-2,3,7,7a-Tetrahydro-7a-methyl-1H-indene-1,5(6H)-dione Valencene

Unit Size 1g 1g

1g 10mL

1g

1mL 1mL 1mL 5g 1g 100mg 100mg 100mg 100mg 200mg 1g 200mg

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

5g 50mg 5g 100mg 100mg 200mg 200mg 100mg 5g 25mL 1g 1g 1g 1g 25g 1g 5g 1g 5g 25mL 1mL 5mL 5mL 5mL 25g 5g 1g 1g 1g 1g 5g 1g 1g 5g

179

Terminal Acetylenes

Materials Chemistry

Synthetic Organic Chemistry

Terminal Acetylenes

B3242

Hydrocarbons

C1522

C1195

HC C CH2CH2Br

C1984

D1724

HC C CH2CH2CH2Cl

CH3(CH2)3

C1493

Cl CH3

CH C CH

D1326

C C CH2CH2 C CH

HC C

(CH2)4Cl

D0037

HC C

(CH2)6 C CH

CH3(CH2)7

C CH

C CH

B1114

D0997

H0440

H0483

H0048

CH3 CH3

C C CH

CH3(CH2)9

C CH

CH3(CH2)14 C CH

HC C

(CH2)3 C CH

CH3(CH2)4 C CH

CH3

H0433

CH3(CH2)13

H0140

C CH

N0301

CH3(CH2)6

M0271

CH3(CH2)3

C CH

O0128

C CH

P0068

CH3(CH2)15

C CH

CH CH2CH2 C CH

HC C

CH3

CH CH2 C CH

O0050

(CH2)4 C CH

P1273 P0810

HC C CH2Br

N0406

CH3

CH3 CH3

O0147

P1272 P0484

CH3CH2CH2 C CH

M0269

HC C CH2Cl

180

(CH2)5 C CH

P0356

CH3(CH2)5

C CH

P1881

CH3(CH2)12 C CH

T0761

CH3

C CH

U0033

CH3(CH2)8

HC C

C CH

Availability or specification of the listed products are subject to change without prior notice.

CH3(CH2)11 C CH

Terminal Acetylenes

4-Bromo-1-butyne 3-Chloro-1-butyne 6-Chloro-1-hexyne 5-Chloro-1-pentyne Cyclopropylacetylene 1,5-Decadiyne 1,9-Decadiyne 1-Decyne 3,3-Dimethyl-1-butyne 1-Dodecyne 1-Heptadecyne 1,6-Heptadiyne 1-Heptyne 1-Hexadecyne 1-Hexyne 5-Methyl-1-hexyne 4-Methyl-1-pentyne 1,8-Nonadiyne 1-Nonyne 1-Octadecyne 1,7-Octadiyne 1-Octyne 1-Pentadecyne 1-Pentyne Propargyl Bromide (80% in Toluene, ca. 9.2mol/L) (stabilized with MgO) Propargyl Bromide (stabilized with MgO) Propargyl Chloride (70% in Toluene, ca. 9.2mol/L) Propargyl Chloride Propyne (ca. 3-4% in Heptane) 1-Tetradecyne 1-Undecyne

Unit Size

B4521

5mL 10mL 5mL

25mL

5mL 25mL

25g 25g

100g 100g 25g

5mL

B3701

OCH2 C CH

5g 5g 25mL 25mL 25g 5mL 5mL 25mL 100mL 25mL 1g 5mL 25mL 5mL 250mL 5mL 5mL 5mL 5mL 5mL 25mL 250mL 5mL 25mL 500g 500g 250g 25mL 200g 25mL 5mL

1g 5mL 5mL 5g 1mL

Materials Chemistry

Product Name

B3242 C1195 C1493 C1522 C1984 D1724 D1326 D0037 B1114 D0997 H0440 H0483 H0048 H0433 H0140 M0271 M0269 N0406 N0301 O0128 O0147 O0050 P0356 P0068 P1272 P0484 P1273 P0810 P1881 T0761 U0033

Synthetic Organic Chemistry

Product No.

B2301 Br

(CH2)3CH3

C CH

C CH

Hydrocarbons having Benzene Ring OCH2 C CH

C2670

D2496 Cl

D2151

D4233

E0749

C CH

C CH

CH2CH3 C CH

HC C

C CH

C CH

E0603

E0196 OCH3

C CH

C CH

E0654 C CH

F0470

E0564 C CH

C CH

C CH F

C CH

E0933

(CH2)5CH3

F

E0563

E0967

E0750

C CH

E0939 C CH

C CH

C CH C C

(CH2)4CH3

C CH

CH2CH2CH3

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

181

Terminal Acetylenes

Synthetic Organic Chemistry

E0665

E0655 CH3

C CH

P2226

E0626 CH3

C CH

C CH

CF3

P2227 CH2OCH2 C CH

P0358

P1956 CH2CH2 C CH

P2190

T3151

CH2 C CH

T2760 C CH

OCH2 C CH

C CH

OCH2 C CH HC C

C

C CH

HC C

C CH

Materials Chemistry

C CH

T3135 OCH2 C CH

HC C CH2O

OCH2 C CH

Product No.

Product Name

B4521 B3701 B2301 C2670 D2496 D2151 D4233 E0749 E0603 E0196 E0654 F0470 E0564 E0933 E0563 E0967 E0750 E0939 E0665 E0655 E0626 P0358 P1956 P2226 P2227 P2190 T3151 T2760 T3135

1,3-Bis(2-propynyloxy)benzene 1-Bromo-4-ethynylbenzene 1-Butyl-4-ethynylbenzene 1-Chloro-4-ethynylbenzene 1,3-Diethynylbenzene 1,4-Diethynylbenzene 4,4'-Diethynylbiphenyl 1-Ethyl-4-ethynylbenzene 4-Ethynylanisole Ethynylbenzene 1-Ethynyl-2-fluorobenzene 1-Ethynyl-4-fluorobenzene 1-Ethynyl-4-hexylbenzene 2-Ethynylnaphthalene 1-Ethynyl-4-pentylbenzene 1-Ethynyl-4-(phenylethynyl)benzene 1-Ethynyl-4-propylbenzene 1-Ethynylpyrene 3-Ethynyltoluene 4-Ethynyltoluene 1-Ethynyl-4-(trifluoromethyl)benzene 4-Phenyl-1-butyne 3-Phenyl-1-propyne (stabilized with BHT) 1-[(2-Propynyloxy)methyl]pyrene 1-(2-Propynyloxy)naphthalene 2-(2-Propynyloxy)naphthalene Tetrakis(4-ethynylphenyl)methane 1,3,5-Triethynylbenzene 1,3,5-Tris(2-propynyloxy)benzene

Unit Size 200mg 1g 1g 5g 5g 25g 1g 5g 1g 5g 1g 5g 200mg 1g 5g 25g 1g 5g 25mL 100mL 500mL 5g 1g 5g 5g 25g 100mg 5g 25g 200mg 1g 5g 25g 200mg 1g 1g 5g 25g 5g 25g 1g 5g 5mL 1g 5g 200mg 1g 1g 5g 200mg 1g 100mg 1g 1g 5g 200mg 1g

B4007

Carboxylic Acids & Their Derivatives

182

P1038 O

HC

C

O OH

HN

D4616

Boc

O

CH3

HC C C O C CH3 CH3

Availability or specification of the listed products are subject to change without prior notice.

HC C CH2CH

C OCH2CH3 C OCH2CH3 O

Terminal Acetylenes

H0823

P0529

H0964

H0882

H0905

HC C CH C OCH2CH3 OH

P0528

O HC C C OCH2CH3

P0497

O

CH3

OH C

HC C CH2CH2CH2 C OH

O HC C CH C OH OH

CH

U0054

O

O

HC C C OCH3

O

HC C C OH

HC C

Product Name

B4007 P1038 D4616 H0823 P0529 H0964 H0882 H0905 P0528 P0497 U0054

N-(tert-Butoxycarbonyl)-L-propargylglycine tert-Butyl Propiolate Diethyl 2-Propynylmalonate Ethyl 2-Hydroxy-3-butynoate Ethyl Propiolate 2-Hexyl-4-pentynoic Acid 5-Hexynoic Acid 2-Hydroxy-3-butynoic Acid Methyl Propiolate Propiolic Acid 10-Undecynoic Acid

(CH2)8

C OH

Unit Size

5mL 5g 5g 100mg 5mL 5g 1g

B2909

B2910

HC

Alcohols

HC C CH2CH2OH

C

CH3

HC

C

C

CH3

HC C

D1266

(CH2)8OH

OH

D2495

E0272

CH3 CH3

D0737 CH3

CHCH2CH2 C C CH

H0823

CH3(CH2)3

C C CH

E0297

E0548 HO

CH3

CH C C CH OH

OH

E0270 O

E0273 CH2CH3

CH2CH3

HC C CH C OCH2CH3

CH3(CH2)3

CH CH C CH

CH3CH2

OH

OH

OH

CH3 CH3

CH3

CHCH2 C C CH

OH

CH2CH3 HC C C OH

D1276 CH3

CH3

H0455

CH3 OH

OH

D3710

1g 25g 5g 1g 25mL 25g 25g 1g 25mL 25g 5g

5g 1g

B0799

HC

Materials Chemistry

Product No.

B0750 B1001

Synthetic Organic Chemistry

O

O

H0141

C C CH OH

H0687

C CH CH3(CH2)3

CH OH

HC C

C CH

CH3CH2CH2

CH C CH OH

HC C

(CH2)4OH

OH

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

183

Terminal Acetylenes

Synthetic Organic Chemistry

H0462

H0905

HC C CH2 CH CH2CH3 OH

M0180 O

M0860

C C CH

P0818

HC C CH2CH2CH2OH

C

P0220

CH

CH3

P0069

C

CH

HC C CH2OH

HC C

C

CH3

OH

P0536

HC C CH2 CH CH3 OH

HC C C CH CH2 OH

O0196

OH

P0817

CH3

CH CH2 CH C CH OH

CH3

OH

Materials Chemistry

CH3

O0235

CH3OCH2 C CH

M1312

CH3

HC C C CH3 OH

CH3 CH3CH2

CH3

HC C CH C OH OH

M0396

M0961

CH

OH

U0055

HC C

(CH2)9OH

OH

184

Product No.

Product Name

B0799 B2909 B2910 B0750 B1001 D3710 D1266 D0737 D1276 D2495 E0272 H0823 E0270 E0273 E0297 E0548 H0455 H0141 H0687 H0462 H0905 M0180 M0961 M1312 M0396 M0860 O0235 O0196 P0069 P0817 P0818 P0220 P0536 U0055

3-Butyn-1-ol (R)-(+)-3-Butyn-2-ol (S)-(-)-3-Butyn-2-ol 3-Butyn-2-ol (55% in Water, ca. 7.5mol/L) 3-Butyn-2-ol 9-Decyn-1-ol 3,6-Dimethyl-1-heptyn-3-ol 3,5-Dimethyl-1-hexyn-3-ol 3,4-Dimethyl-1-pentyn-3-ol 1,1-Diphenyl-2-propyn-1-ol 3-Ethyl-1-heptyn-3-ol Ethyl 2-Hydroxy-3-butynoate 4-Ethyl-1-octyn-3-ol 3-Ethyl-1-pentyn-3-ol 1-Ethynyl-1-cyclohexanol 9-Ethynyl-9-fluorenol 1-Heptyn-3-ol 1-Hexyn-3-ol 5-Hexyn-1-ol 5-Hexyn-3-ol 2-Hydroxy-3-butynoic Acid 2-Methyl-3-butyn-2-ol 5-Methyl-1-hexyn-3-ol 3-Methyl-1-penten-4-yn-3-ol 3-Methyl-1-pentyn-3-ol Methyl Propargyl Ether (S)-1-Octyn-3-ol 1-Octyn-3-ol 1-Pentyn-3-ol 4-Pentyn-1-ol 4-Pentyn-2-ol 1-Phenyl-2-propyn-1-ol 2-Propyn-1-ol 10-Undecyn-1-ol

Unit Size

Availability or specification of the listed products are subject to change without prior notice.

5mL 1g 25mL 5mL

25mL 5g

25mL 5mL 25g 1mL 5mL 5mL 100mg 25mL 5mL 5mL 1g 25mL 5mL 5g 25mL 100mL

25mL 5g 1g 500mL 25mL 5g 5mL 500mL 10mL 25g 5mL 1g 500mL 25mL 500g 5g 5mL 25mL 25mL 5mL 1g 500mL 5mL 25mL 25mL 25mL 5g 250mL 10g 25mL 5mL 25g 500mL 5g

Terminal Acetylenes

B4472

B2393

CH3

HC C C CH3

CH3

T1224

D4275

E1130

E1093

CH3

CH3

HC C

HO

O

P1173

O S C CH

CH3

O

P2171

O

N H

C

(CH2)3CH3 NH2

P1438

CH3(CH2)3 Sn

C CH

(CH2)3CH3

CH3

P2258

O CH3

OCH2CH3

T2387

O

S OCH2 C CH

CH2CH3 C CH

CH2CH3

OCH2CH3

HC C CH2O C NH(CH2)3 Si OCH2CH3 OCH2CH3

O

T1683

CH3CH2 Si

O

B C CH

T1455

HC C

CH3

OH

OCH2CH3 CH

T1750 O

HC

C

O

O

Materials Chemistry

G0445

CH3 N

O

C CH

E0466

O

CH3

C CH

N

N H

S OCH2CH2 C CH O

E1074

C CH

S O CH C CH

CH3

NH2

SO2NH2 O

O

O

HC C CH2NH C O C CH3

Synthetic Organic Chemistry

O

Others

T2046

T1239 CH(CH3)2

(CH3)2CH Si

C CH

CH(CH3)2

CH3 CH3

Si

C CH

CH3

T2992

P

CH2 C CH

HC

C

Br

N

C C

CH

CH

Product No.

Product Name

B4472 B2393 T2046 T1224 D4275 E1130 E1093 E1074 E0466 G0445 P1173 T1455 P2258 P2171 T1750 T2387 T1683 T1239 P1438 T2992

N-(tert-Butoxycarbonyl)propargylamine 3-Butyn-2-one 3-Butynyl p-Toluenesulfonate 1-Butyn-3-yl p-Toluenesulfonate 3,6-Diethynylcarbazole 4-Ethynylbenzenesulfonamide 5-Ethynyl-2'-deoxycytidine 2-Ethynyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Ethynyl p-Tolyl Sulfone Glycidyl Propargyl Ether Propargylaldehyde Diethyl Acetal Propargyl p-Toluenesulfonate 2-Propynyl [3-(Triethoxysilyl)propyl]carbamate 2-Propynylurea Tributylethynyltin Triethylsilylacetylene Triisopropylsilylacetylene Trimethylsilylacetylene Triphenylpropargylphosphonium Bromide Tripropargylamine

Unit Size 1g

200mg 200mg 50mg 200mg 1g 1g 5mL 1g 200mg 1g 1g 5mL 5mL 25mL 5g 1g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

5g 5g 5g 5g 1g 1g 200mg 1g 5g 5g 25mL 5g 5g 1g 5g 5g 25mL 250mL 25g 5g

185

Azide Compounds

Synthetic Organic Chemistry

Azide Compounds

A1786

A0930

A2474 O

SO2N3

Organic Azides

C OH

Materials Chemistry

A2758

O

O

O

CH3 CH3 O

O NH C CH3

A0971

N3 O

A2052

O

CH3 CH3

N3

A1341

A2738

O

N3

O N3

CH3

HN HO

CH CH C H

O

O

S CH2N3 N3

N

NH2

O

O N3

A2524

A2290

A2674

A2729

O HN

F

OH H

S

C OH

C OH NH

H

N H

N3

N3

F

B1111

B3693 O HC

CH

N3CH2

CH3

S0860 O

F

O

OCH3 CH3

O

CH3 OCH3

NO2

O

CH

N3

N3CH2

O

OCH3 CH3

O

CH3 OCH3

N3

D1606

H N OH O

O S

S

N H

OH

N3 N3

N3

CH CH SO3Na NaO3S

.4H2O

T1184 F

N3

O C O N

F

B3790

N3CH2

CH3

O

C O N

186

O

S0952

N3

HC

F

B3694

N3CH2

N3

O N3

OH

N3

N3

N3

O

F

O

(CH2)4

B1110

O

O

F

O

CH3

Si

CH2N3

CH3

Product No.

Product Name

A1786 A0930 A2474 A0971 A2758 A2052 A1341 A2738 A2524 A2290 A2674 A2729 B1110 B1111

4-Acetamidobenzenesulfonyl Azide 5g 25g 4-Azidobenzoic Acid 5g 25g 2-Azido-1,3-bis[(2,2-dimethyl-1,3-dioxan-5-yl)oxy]propane 100mg 4-Azidocinnamaldehyde 5g 4-Azidocoumarin 200mg 3'-Azido-3'-deoxythymidine 1g 5g Azidomethyl Phenyl Sulfide 5g 3-Azidopropylamine 100mg N-(3-Azidopropyl)biotinamide 100mg 4-Azidosalicylic Acid 100mg 1g 4-Azido-2,3,5,6-tetrafluorobenzoic Acid 1g 5-Azidovaleric Acid 200mg 2,6-Bis(4-azidobenzylidene)cyclohexanone (wetted with ca. 30% Water, containing 25g on a dry weight basis) 25g 2,6-Bis(4-azidobenzylidene)-4-methylcyclohexanone (wetted with ca. 30% Water, Price on request containing 25g on a dry weight basis)

Unit Size

Availability or specification of the listed products are subject to change without prior notice.

Azide Compounds

Product Name

B3693 B3694 B3790 D1606 D2580 S0860 S0952 T1184

(2R,3R,5S,6S)-5,6-Bis(azidomethyl)-2,3-dimethoxy-2,3-dimethyl-1,4-dioxane (2S,3S,5R,6R)-5,6-Bis(azidomethyl)-2,3-dimethoxy-2,3-dimethyl-1,4-dioxane Bis[2-(4-azidosalicylamido)ethyl] Disulfide Disodium 4,4'-Diazidostilbene-2,2'-disulfonate Tetrahydrate Dodecylbenzenesulfonyl Azide (soft type) (mixture) N-Succinimidyl 5-Azido-2-nitrobenzoate N-Succinimidyl 4-Azido-2,3,5,6-tetrafluorobenzoate Trimethylsilylmethyl Azide

Unit Size

A2727

A2388

O HN H

PEG Azides

A2500

N3

O

A2728

O

O

NH H S

O

OH

CH3

O O

N H

(CH2)4

O

O

4

N3

O

O 8

O

O

Product Name

A2523 A2727 A2388 A2500 A2728 A2363 A2293 A2294

N-[2-[2-[2-(2-Azidoethoxy)ethoxy]ethoxy]ethyl]biotinamide 25-Azido-2,5,8,11,14,17,20,23-octaoxapentacosane Azido-PEG4-NHS Ester 14-Azido-3,6,9,12-tetraoxatetradecanol 13-Azido-2,5,8,11-tetraoxatridecane 11-Azido-3,6,9-trioxaundecan-1-amine 11-Azido-3,6,9-trioxaundecanoic Acid 11-Azido-3,6,9-trioxaundecanol

O

O

O O

A1678

Ph

O

O

AcHN

O

O

N3

O

O

OH

A1811 O O BnO

N3

A1833 OBn O

O

N3 AcHN

HO

Ph

O N3

O O HO

O N3

NHAc

A1832

Ph

BnO BnO

N

100mg 25mg 100mg 25mg 100mg 25mg 100mg 1g 5g 1g Price on request

NHAc

N3

OH

A1813

Ph

Sugar Azides

AcO AcO

O

A2294

O

N3

4

O

Unit Size

A1812

OAc O

O

O NH2

Product No.

A1616

N3

N3

A2293

O

N3

CH3

N3

A2363

O

100mg 100mg 10mg 25g 25g 10mg 200mg 1g 1g 5g

Materials Chemistry

A2523

Synthetic Organic Chemistry

Product No.

NHAc

G0257

Ph

O

O

O AcO

O

O

HO

O

N3 O

N3 O

OC(CH3)3 HN

Fmoc

OAc O

AcO

O

AcO

O

O

O

N3

OC(CH3)3

CH3 HN

Fmoc

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

187

Azide Compounds

Synthetic Organic Chemistry

A2627

A2172

HO

OH O

HO

O

O

N3

AcHN

D4217 HO AcHN

OH O

HO HO

O

N3

HO

G0330 Ph

OAc O

AcO AcO

AcO

O

N3

OAc

G0373

HO

O HO

O

HO

HO

HO

OH O AcHN HO HO HO

O HO

AcO

O

O

HO

HO

AcO HO O

HO O

HO HO O OH OH O O O HO AcHN

OH NHAc O O O HO AcHN OH

O

O OAc

O

OCH3

N3

G0403

COONa HO O O HO

OH O HO

O HO

OH O AcHN HO HO HO

HO HO

N3

O

OCH3

HO

OH O HO

OH O O

AcHN

O HO NaO3SO

O

HO HO

HO

O AcHN

N3

O

O N3

O

COONa HO O O HO

OH O HO

O HO

OH HO O O AcHN

M1637

Ph

O O

O

OCH3

N3

OCH3

T2196

AcO AcO

O O

OH O

OH O

O HO

O

HO

OH O HO

OH O

O HO

HO

HO HO

O

OH O O AcHN HO

N3

OH HO O O AcHN

OH O O AcHN HO

OH O

O

AcHN

M1617

T1731

O O HO

O O N3

OCH3

HO BnO

AcO

OBn O O

OCH3

N3

OAc O

AcO N3

OAc

T1733 AcO

OAc O OAc

AcO AcO

N3

N3 O OAc

Product No.

Product Name

A1812 A1813 A1811 A1616 A1678 A1833

2-Acetamido-3-O-allyl-4,6-O-benzylidene-2-deoxy-β-D-glucopyranosyl Azide 1g 2-Acetamido-3-O-benzyl-4,6-O-benzylidene-2-deoxy-β-D-glucopyranosyl Azide 1g 1g 5g 2-Acetamido-4,6-O-benzylidene-2-deoxy-β-D-glucopyranosyl Azide 2-Acetamido-3,4,6-tri-O-acetyl-2-deoxy-β-D-glucopyranosyl Azide 1g 5g 2-Acetamido-3,4,6-tri-O-benzyl-2-deoxy-β-D-glucopyranosyl Azide 1g 5g O-(2-Azido-4,6-O-benzylidene-2-deoxy-α-D-galactopyranosyl)-N-[(9H-fluoren-9-ylmethoxy)carbonyl]100mg L-serine tert-Butyl Ester O-(2-Azido-4,6-O-benzylidene-2-deoxy-α-D-galactopyranosyl)-N-[(9H-fluoren-9-ylmethoxy)carbonyl]100mg L-threonine tert-Butyl Ester 2-[2-(2-Azidoethoxy)ethoxy]ethyl 2,3,4,6-Tetra-O-acetyl-D-galactopyranoside 1g 5g 2-Azidoethyl 2-Acetamido-2-deoxy-β-D-galactopyranoside Price on request 500mg 2-Azidoethyl 2-Acetamido-2-deoxy-β-D-glucopyranoside 2-Azidoethyl β-D-Glucopyranoside 1g 2-Azidoethyl 2,3,4,6-Tetra-O-acetyl-β-D-glucopyranoside 1g 5g Disialylnonasaccharide β-Ethylazide Price on request Gal[2346Ac]β(1-3)GalN3[46Bzd]-β-MP 1g 5g 1g 5g Gal[2346Ac]β(1-3)GlcN3[46Bzd]-β-MP GalNAcβ(1-3)GlcNAcβ-Ethylazide Price on request Gb3-β-ethylazide Price on request GlcA[3S]β(1-3)Galβ(1-4)GlcNAcβ(1-2)Manα-Ethylazide Price on request GlcNAcβ(1-2)Manα-1-Ethylazide 100mg HNK-1 Ethylazide Price on request LacDiNAc Dimer Ethylazide Price on request 1g 4-Methoxyphenyl 3-O-Allyl-2-azido-4,6-O-benzylidene-2-deoxy-β-D-galactopyranoside

A1832 G0257 A2627 A2172 A2267 A2377 D4217 G0330 G0309 G0373 G0403 G0372 G0337 H1333 L0237 M1643

N3

L0237

Ph Ph

O

HO

N3

M1638

O

OH O

HO

H1333

O

M1643

O

O

HO

AcHN HO N3

OAc

HO O O

OH O

O O

OAc Ph O

N3

G0337

O

188

O O

AcO

HO O

O HO O

COOH O

O HO

G0372

O

O

OAc O

COOH O

OH HO AcHN

HO NaO3SO

A2377

G0309 OH

HO

HO

Materials Chemistry

OH O

HO HO

N3

AcHN

A2267

Unit Size

Availability or specification of the listed products are subject to change without prior notice.

N3

Azide Compounds

Product Name

M1638 M1637 M1617 T1731 T2196 T1733

4-Methoxyphenyl 3-O-Allyl-2-azido-4,6-O-benzylidene-2-deoxy-β-D-glucopyranoside 4-Methoxyphenyl 2-Azido-4,6-O-benzylidene-2-deoxy-β-D-glucopyranoside 4-Methoxyphenyl 2-Azido-3,6-di-O-benzyl-2-deoxy-β-D-glucopyranoside 1,3,4,6-Tetra-O-acetyl-2-azido-2-deoxy-α-D-galactopyranose 1,3,4,6-Tetra-O-acetyl-2-azido-2-deoxy-β-D-glucopyranose 1,3,4,6-Tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranose

Unit Size Synthetic Organic Chemistry

Product No.

1g 5g 1g 100mg 200mg 1g 100mg 1g

Materials Chemistry

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

189

Fullerenes Fullerene is a spherical carbon compound and is an allotrope of carbon such as diamond, graphite and carbon nanotubes. Fullerenes of C60, C70 and C84 are well known. They are isolable carbon compounds in a sole molecular species. Among them, the C60 is a representative species. Kroto, Smalley and Curl . first observed the C60 in which the 60 carbon atoms consist of 12 five-membered rings and 20 six-membered rings.1) Kroto, Smalley and Curl won their joint Nobel prizes in chemistry in 1996 for their contributions. Osawa predicted existence of fullerene in 1970, earlier than the first observation of fullerene.2) The most specific feature of fullerene is that it is an excellent electron acceptor. Any fullerenes are n-type semiconductors, which are suitable for organic electronic materials with electron carriers. Rubidium- and cesium-doped fullerenes can be superconductors with electron carriers. These superconducting transitions occur at more than 30 K.3,4)

Materials Chemistry

Synthetic Organic Chemistry

Fullerenes

OCH3 O

C60

[60]PCBM

[B1641, B1660]

[M2088]

C70

[60]ICBA

[B1694]

[I0900]

Addition reactions and other chemical modifications of fullerenes easily produce fullerene derivatives. Precise structure analyses of these derivatives are possible because they are molecular species. Nonderivatized fullerenes are poorly soluble in similarity to the other nanocarbon materials. However, we can introduce soluble functional groups to form solution-processible electronic materials. Phenyl-C61-butyric acid methyl ester ([60]PCBM) and indene-C60 bisadduct (ICBA) are useful organic semiconductors for fabricating a solution-processible electronic device.5,6) These fullerene derivatives are n-type organic semiconductors for organic photovoltaics (OPV) by mixing with a p-type conjugated polymer.7) An application of a fullerene derivative for organic transistors was also reported.8) A complexation of C60 with tetrakis(dimethylamino)ethylene (TDAE) gives a charge transfer complex (TDAE-C60), which is an organic magnet at low temperature.9) Although a chemical modification of the outer surface of fullerene provides PCBM or ICBA, we can introduce a small component to the inner side of fullerene. For instance, fullerenes can encapsulate a metal atom on the inner side, when the fullerenes are produced in the presence of the metal. This is the so-called metal-encapsulated fullerene described as [email protected] The encapsulation modifies the electronic state10) and chemical reactivity of fullerene.11) On the other hand, water-encapsulated fullerene ([email protected]) was also reported. A publication described that an organic synthetic procedure gave open-caged C60 which could then encapsulate one water molecule. A following chemical modification could close the cage to from water-encapsulated fullerene [email protected])

190

Availability or specification of the listed products are subject to change without prior notice.

Fullerenes

B1642

B1694

C2415

I0900 CH3 N

P2013

P2014

P2015 O

O (CH2)3 C O(CH2)3CH3

(CH2)3 C O(CH2)7CH3

Synthetic Organic Chemistry

B1641 B1660

(CH2)11CH3

M2088

M2550

O (CH2)3 C O(CH2)11CH3

OCH3

OCH3 O

O

Materials Chemistry

B4576 OCH3 O

O OCH3

mixture of isomers

Product No.

Product Name

B1641 B1660 B1642 B1694 C2415 I0900 P2013 P2014 P2015 M2088 M2550 B4576

Fullerene C60 (pure) Fullerene C60 Fullerene Extract, C60 (contains ca. 20% C70) Fullerene C70 C60MC12 ICBA [60]PCB-C4 ([6,6]-Phenyl-C61-butyric Acid Butyl Ester) [60]PCB-C8 ([6,6]-Phenyl-C61-butyric Acid n-Octyl Ester) [60]PCB-C12 ([6,6]-Phenyl-C61-butyric Acid Dodecyl Ester) [60]PCBM (Methyl [6,6]-Phenyl-C61-butyrate) [70]PCBM (Methyl [6,6]-Phenyl-C71-butyrate) (mixture of isomers) Bis-PCBM (mixture of isomers)

Unit Size 100mg 100mg 100mg

1g 1g 1g 100mg 100mg 50mg 100mg 100mg 100mg 100mg 50mg 50mg

References 1) 2) 3) 4) 5) 6) 7) 8) 9) 10) 11) 12)

1985, H. W. Kroto, J. R. Heath, S. C. O’Brien, R. F. Curl, R. E. Smalley, , 162. 1970, E. Osawa, , 854. 1991, K. Tanigaki, T. W. Ebbesen, S. Saito, J. Mizuki, J. S. Tsai, Y. Kubo, S. Kuroshima, , 222. A. Y. Ganin, Y. Takabayashi, Y. Z. Khimyak, S. Margadonna, A. Tamai, M. J. Rosseinsky, K. Prassides, . 2008, , 367. J. C. Hummelen, B. W. Knight, F. LePeq, F. Wudl, J. Yao, C. L. Wilkins, . 1995, , 532. Y. He, H.-Y. Chen, J. Hou, Y. Li, . 2010, , 1377. Review: S. Günes, H. Neugebauer, N. S. Sariciftci, . 2007, , 1324. T.-W. Lee, Y. Byun, B.-W. Koo, I.-N. Kang, Y.-Y. Lyu, C. H. Lee, L. Pu, S. Y. Lee, . 2005, , 2180. 2000, B. Narymbetov, A. Omerzu, V. V. Kabanov, M. Tokumoto, H. Kobayashi, D. Mihailovic, , 883. Y. Matsuo, H. Okada, M. Maruyama, H. Sato, H. Tobita, Y. Ono, K. Omote, K. Kawachi, Y. Kasama, . 2012, , 3784. H. Kawakami, H. Okada, Y. Matsuo, . 2013, , 4466. 2011, K. Kurotobi, Y. Murata, , 613.

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191

Materials Chemistry

Synthetic Organic Chemistry

Carbon Nanotubes

Carbon Nanotubes A carbon nanotube (CNT) has a cylindrical structure with a nanoscale diameter that is like a rolled graphene sheet. Iijima first observed a CNT in 1991.1) A CNT consists of only sp2 carbons similar to fullerenes. There are diverse CNTs on the basis of their length, diameter of the nanotube, state of chirality, and number of the layer. The variety of these structures provides various band structures and metallic and semiconducting properties.2,3) A normal synthetic procedure gives a mixture of semiconducting CNTs in 2/3 and metallic CNTs in 1/3, because rolling a carbon sheet occurs randomly. Since we need to obtain the semiconducting CNT in pure form in order to utilize the semiconductivity, improved synthetic procedure and efficient purification of CNT are further required.4-7) Moreover, CNTs have high physical durability, high electrical and thermal conductivity, and are light and flexible. On the basis of such excellent characteristics, CNTs are expected to be field-effect transistor (FET) materials, nanoscale wire materials, electron emission sources, optical communication switches, chemical sensors, high strength composites, and thermal devices.8-10) CNTs can enclose nanoscale molecules and atoms in the internal space, because of the cylindrical structure. For instance, there is a fullerene-enclosed CNT, the so-called‘peapod’.11) In addition, CNTs can enclose metal, water, and molecular oxygen. Properties of the enclosed water in the CNT are different from those of bulk water.12,13) An organic dye (eg. squarylium) can be easily enclosed within the internal space of CNTs in solution. In this case, the enclosed squarylium dye absorbs light and then an energy transfer (sensitization) to the outer CNT occurs.14) Hydrogen storage using CNTs is expected to be used in the development of a fuel cell.15)

C60Peapod

[email protected] Single-WalledCarbonNanotube (SWCNT)

192

Availability or specification of the listed products are subject to change without prior notice.

Carbon Nanotubes

Product Name

C3133 C2143 C2149 C2148 C2150 C2153 C2152 C2155 C2154 C2157 C2156 C2159 C2158 C2151 C2147 C2146

Carbon Nanotube Single-walled (>85%) below 3nm(Average diam.), over 5μm(Average length) 200mg Carbon Nanotube Double-walled (>50%) below 5nm(diam.), 5-15μm(length) 200mg Carbon Nanotube Multi-walled below 10nm(diam.), 1-2μm(length) Price on request Carbon Nanotube Multi-walled below 10nm(diam.), 5-15μm(length) 1g 1g 5g Carbon Nanotube Multi-walled 10-20nm(diam.), 5-15μm(length) Carbon Nanotube Multi-walled 10-30nm(diam.), 1-2μm(length) 1g Carbon Nanotube Multi-walled 10-30nm(diam.), 5-15μm(length) 1g Carbon Nanotube Multi-walled 20-40nm(diam.), 1-2μm(length) 1g Carbon Nanotube Multi-walled 20-40nm(diam.), 5-15μm(length) 1g 5g 1g Carbon Nanotube Multi-walled 40-60nm(diam.), 1-2μm(length) Carbon Nanotube Multi-walled 40-60nm(diam.), 5-15μm(length) 1g 5g Carbon Nanotube Multi-walled 60-100nm(diam.), 1-2μm(length) 1g Carbon Nanotube Multi-walled 60-100nm(diam.), 5-15μm(length) 1g 5g Carbon Nanotube Aligned Multi-walled 10-20nm(diam.), 5-15μm(length) 1g Carbon Nanotube Bundled Multi-walled below 10nm(diam.), 5-15μm(length) (allowable temperature limit : 620℃) 200mg Carbon Nanotube Herringbone 10-20nm(diam.), 5-15μm(length) 200mg

Unit Size

Synthetic Organic Chemistry

Product No.

1) 2) 3) 4) 5) 6) 7) 8) 9) 10) 11) 12) 13) 14) 15)

1991, S. Iijima, , 56. J. Kim, A. J. Page, S. Irle, K. Morokuma, . 2012, , 9311. 2011, Review: Y. Miyato, , 61. M. Kawai, H. Kyakuno, T. Suzuki, T. Igarashi, H. Suzuki, T. Okazaki, H. Kataura, Y. Maniwa, K. Yanagi, . 2012, , 9545. 2012, , 1973. I. Ibrahim, A. Bachmatiuk, J. H. Warner, B. Büchner, G. Cuniberti, M. H. Rümmeli, B. Liu, W. Ren, S. Li, C. Liu, H.-M. Cheng, . 2012, , 2409. H. Liu, D. Nishide, T. Tanaka, H. Kataura, . 2011, , 1313/1. 2008, Review: K. Balasubramanian, E. J. H. Lee, R. T. Weitz, M. Burghard, K. Kern, , 633. J. Park, Y. Kim, G.-T. Kim, J. S. Ha, . 2011, , 4159. 2013, , 2800. N. J. Kybert, M. B. Lerner, J. S. Yodh, G. Preti, A. T. C. Johnson, J. H. Warner, A. A. R. Watt, L. Ge, K. Porfyrakis, T. Akachi, H. Okimoto, Y. Ito, A. Ardavan, B. Montanari, J. H. Jefferson, N. M. Harrison, H. Shinohara, G. A. D. Briggs, . 2008, , 1005. H. Kyakuno, K. Matsuda, H. Yahiro, Y. Inami, T. Fukuoka, Y. Miyata, K. Yanagi, Y. Maniwa, H. Kataura, T. Saito, M. Yumura, S. Iijima, . 2011, , 244501. 2013, J. M. H. Kroes, F. Pietrucci, A. Curioni, R. Jaafar, O. Gröning, W. Andreoni, , 1948. K. Yanagi, K. Iakoubovskii, H. Matsui, H. Matsuzaki, H. Okamoto, Y. Miyata, Y. Maniwa, S. Kazaoui, N. Minami, H. Kataura . 2007, , 4992. E. Tylianakis, G. K. Dimitrakakis, F. J. Martin-Martinez, S. Melchor, J. A. Dobado, E. Klontzas, G. E. Froudakis, Int. 2014, , 9825.

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193

Materials Chemistry

References

Materials Chemistry

Synthetic Organic Chemistry

Graphene & Graphene Oxide

Graphene & Graphene Oxide Graphene, which is one of the nanocarbon materials, consists of all six-membered rings with sp2 carbons having a two-dimensional sheet structure. Graphene has been known for long time, since graphite is formed by combination of graphenes with van der Waals force. However, details of the properties were unclear until late years, because an isolation procedure of graphene from graphite was not well developed for long time. Geim and Novoselov . in 2004 successfully isolated a thin-flake graphene by a simple procedure. They used a tape to peel off a graphene layer from highly oriented pyrolytic graphite (HOPG) and then the peeled graphene layer is stuck on a substrate. After this observation,1) studies of graphene have proved the particular characteristics of electronic, mechanical, and chemical properties. Geim and Novoselov won their joint Nobel prizes in physics in 2010 for their contributions. The most characteristic feature of graphene is its electrical property. The electron mobility in the graphene layer is 100 times greater than that of silicon.2) Accordingly, we can expect to develop a transistor with high-mobility and low-power consumption. Graphene may be promising for a next generation channel material that is useful for LSI (large-scale integration). In addition, the physical strength of graphene is 100 times greater than that of iron. The current density tolerance is much better than that of copper, thus it is expected to be an electrical wire transporting large currents.3) Electrons in the graphene behave as massless Dirac fermions as similar to neutrinos,4) and demonstrate a quantum Hall effect at room temperature.5) Graphene is an ideal material for spintronics, since there are small spin orbit interactions and the negligible nuclear magnetic moment of carbon. Hybridization of graphene and a ferromagnetic material is developed for the application of an information processor using the electron spin (spintronics device).6) COOH OH HOOC

OH O

Graphene [G0438, G0441, G0442]

O

O

OH OH

Graphene oxide [G0443, G0444]

The fabrication procedure for graphene is peeling off the layer from HOPG, a chemical vapor deposition (CVD)7) as well as reduction of a graphene oxide (GO).8) There are various synthetic methods of making GO, and the properties and applications depend on the degree of oxidation. GO disperses in water and several polar solvents, because the structure of GO normally includes hydroxyl, epoxy, and carboxyl groups on the graphene sheet. Accordingly, a GO thin film can be fabricated on a substrate by a solutionprocess. The reduction of GO provides a reduced graphene oxide (rGO), but it is not a perfect graphene. The rGO contains a few oxygen components and defects on the graphene structure. Although GO is an insulator because there are sp3 carbon atoms, rGO is conductive. Therefore the rGO is expected to be an electrode material. A water dispersion of GO is used as a lubricant to reduce friction on metal surfaces.9) GO-supported metal catalysts were developed for a cross-coupling reaction and hydrogenation.10,11) We can introduce several functional groups on GO because there are oxygen-based groups. These GO derivatives may be useful for luminescent materials and biosensors.12,13)

194

Product No.

Product Name

G0441 G0442 G0438 G0443 G0444

Graphene Nanoplatelets 6-8nm(thick), 5μm(wide) Graphene Nanoplatelets 6-8nm(thick), 15μm(wide) Graphene Nanoplatelets 6-8nm(thick), 25μm(wide) Graphene Oxide Graphene Oxide (10mg/mL, Dispersion in Water)

Unit Size 5g 5g 5g

25g 25g 25g 100mg 5mL 25mL

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

Graphene & Graphene Oxide

References Synthetic Organic Chemistry

1) K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, Y. Zhang, S. V. Dubonos, I. V. Grigorieva, A. A. Firsov, 2004, , 666. 2) K. I. Bolotin, K. J. Sikes, Z. Jiang, M. Klima, G. Fudenberg, J. Hone, P. Kim, H. L. Stormer, . 2008, , 351. 2009, 3) A. K. Geim, , 1530. 4) K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, M. I. Katsnelson, I. V. Grigorieva, S. V. Dubonos, A. A. Firsov, 2005, , 197. 2005, 5) Y. Zhang, Y.-W. Tan, H. L. Stormer, P. Kim, , 201. 6) D. Pesin, A. H. MacDonald, . 2012, , 409. 7) X. Zhang, L. Wang, J. Xin, B. I. Yakobson, F. Ding, . 2014, , 3040. 8) C. K. Chua, M. Pumera, . 2014, , 291. 2014, 9) H. Kinoshita, Y. Nishina, A. A. Alias, M. Fujii, , 720. 2014, , 6501. 10) S. Yamamoto, H. Kinoshita, H. Hashimoto, Y. Nishina, 11) N. Morimoto, S. Yamamoto, Y. Takeuchi, Y. Nishina, . 2013, , 15608. 2013, , 1119. 12) K. Furukawa, Y. Ueno, E. Tamechika, H. Hibino, 13) G. Gou, R. Ren, S. Li, S. Guo, Z. Dong, M. Xie, J. Ma, . 2013, , 3861.

Materials Chemistry

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

195

Materials Chemistry

Synthetic Organic Chemistry

Nanodiamonds

Nanodiamonds Diamond, an allotrope of carbon, has excellent hardness, coefficient of friction, thermal conductivity, insulation characteristics, and refractive index. Large and highly pure diamond is good for use as jewelry. Furthermore, the major industrial application of diamond is for cutting and polishing tools, because it is the hardest of natural products. However, diamond is not workable enough because of its hardness so there is a limitation for industrial use of a large diamond. Nanodiamond (ND) is a nanoparticle having the crystal structure of diamond, and it has excellent properties of normal diamond. ND is artificially synthesized and is useful for polishing tools and additives of engine oil.

Nanodiamond (ND) We can modify the surface of ND by introducing carboxyl and amino groups. These groups are further converted by a chemical modification to functionalize the ND particle.1-3) Non-modified ND can be dispersed in water, but coheres in organic solvents. On the other hand, a functionalized ND particle with alkyl groups can be dispersed in organic solvents. We can modify a glass surface with ND that is functionalized with a silane coupling reagent.4)

ND

CO2H

SOCl2

ND

COCl

C18H37NH2

CONHC18H37

ND

[N0969] HO2C

ND

NH2

N3

ND

HNOC

N3

[N0968]

An application of ND is extended for biology and medical use5,6) because it is a harmless nanoparticle in-vivo. Since a diamond with a complex defect (NV) containing nitrogen (N) and vacancy (V) shows fluorescence,7) we can monitor movements and structural changes of a biological molecule on a microscope using the NV diamond as a fluorescent labeling reagent.8-10) We can easily detect fluorescent behavior in a complex atmosphere in-vivo, because ND is chemically stable. A publication described that functionalization of ND also showed fluorescent behavior without NV defects.11) Protein- and biotinsupported ND were reported in order to enhance affinity toward a biological molecule.12,13) These modified NDs are expected to be used for a drug delivery system. Product No.

Product Name

N0962 N0968 N0969

Nanodiamond (particle size : 99.9%) Picene (purified by sublimation) Tetrabutylammonium Bis(1,3-dithiole-2-thione-4,5-dithiolato)nickel(III) Complex Tetrabutylammonium Bis(maleonitriledithiolato)nickel(III) Complex 3,3',5,5'-Tetra-tert-butyl-4,4'-diphenoquinone Tetrabutylphosphonium Bis(1,3-dithiole-2-thione-4,5-dithiolato)nickel(III) Complex Tetracyanoethylene 11,11,12,12-Tetracyanonaphtho-2,6-quinodimethane 7,7,8,8-Tetracyanoquinodimethane (purified by sublimation) 7,7,8,8-Tetracyanoquinodimethane Tetrafluoro-1,4-benzoquinone Tetrafluorotetracyanoquinodimethane (purified by sublimation) Tetrathiafulvalene - 7,7,8,8-Tetracyanoquinodimethane Complex 2,4,7-Trinitro-9-fluorenylidenemalononitrile

Unit Size

S0838

T1269

(CH2)3CH3

T1803

(CH2)3CH3

CH3(CH2)3 N

T1271

T0839

(CH2)3CH3 I3

CH3(CH2)3 N

(CH2)3CH3 BF4

(CH2)3CH3

CH3(CH2)3 N

T1284

(CH2)3CH3

(CH2)3CH3 CH3(CH2)3

(CH2)3CH3 PF6

(CH2)3CH3

(CH2)3CH3

N

(CH2)3CH3

(CH2)3CH3

SCN

CH3(CH2)3 N

(CH2)3CH3 Br3

(CH2)3CH3

T0983 CH2CH3

CH2CH3 CH3CH2 N CH2CH3 BF4

CH2CH3

CH2CH3

(CH2)3CH3

(CH2)3CH3

(CH2)3CH3 AuI 2

T1278

CH3CH2 N CH2CH3 ClO4

(CH2)3CH3 CH3(CH2)3 N

CH3(CH2)3 N

(CH2)3CH3 ReO4

(CH2)3CH3

(CH2)3CH3

228

(CH2)3CH3

(CH2)3CH3 AuBr2

T1279

(CH2)3CH3 Cl2Br

T2648 T0914 (CH2)3CH3

(CH2)3CH3 ClO4

(CH2)3CH3

(CH2)3CH3

(CH2)3CH3

T0836

CH3(CH2)3 N

CH3(CH2)3 N

CH3(CH2)3 N

(CH2)3CH3

T1357

(CH2)3CH3

(CH2)3CH3 AuCl 2

(CH2)3CH3

(CH2)3CH3 BrI2

(CH2)3CH3

T1186

CH3(CH2)3 N

(CH2)3CH3

CH3(CH2)3 N

Na

NC

(CH2)3CH3

(CH2)3CH3 IBr2

T1261

(CH2)3CH3

N

T1273

CH3(CH2)3 N

T1270

NC

Supporting Electrolytes for Electrocrystallization

100mg 500mg 100mg 100mg 100mg 1g 100mg 1g 100mg 1g 5g 1sample 25g 500g 100mg 100mg 1g 100mg 1g 1g 1g 5g 25g 100mg 1g 5g 5g 25g 1g 5g 100mg 1g 1g 1g 5g

Product No.

Product Name

S0838 T1270 T1261 T1269 T1273 T1186

Sodium Dicyanamide Tetrabutylammonium Bromodiiodide Tetrabutylammonium Dibromoaurate Tetrabutylammonium Dibromoiodide Tetrabutylammonium Dichloroaurate Tetrabutylammonium Dichlorobromide

Unit Size 25g

100g 1g 1g 1g 10g 100mg 25g

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Molecular Conductors

Product Name

T1357 T1279 T0836 T1803 T2648 T0914 T1278 T1284 T1271 T0839 T0983

Tetrabutylammonium Diiodoaurate Tetrabutylammonium Hexafluorophosphate Tetrabutylammonium Perchlorate Tetrabutylammonium Perrhenate Tetrabutylammonium Tetrafluoroborate Tetrabutylammonium Tetrafluoroborate Tetrabutylammonium Thiocyanate Tetrabutylammonium Tribromide Tetrabutylammonium Triiodide Tetraethylammonium Perchlorate Tetraethylammonium Tetrafluoroborate

Unit Size 100mg 25g 25g 100g 1g 25g 25g

100g 25g 100g 5g

Synthetic Organic Chemistry

Product No.

1g 250g 500g 5g 25g 500g 250g 500g 25g 25g 25g

References

12) 13) 14) 15) 16)

1954, H. Akamatu, H. Inokuchi, Y. Matsunaga, , 168. F. Wudl, D. Wobschall, E. J. Hufnagel, . 1972, , 670. D. Jérome, A. Mazaud, M. Ribault, K. Bechgaard, . 1980, , 95. T. Mori, . 2004, , 4947. R. P. Shibaeva, E. B. Yagubskii, . 2004, , 5347. 1994, , 1. H. Mori, P. Batail, K. Boubekeur, M. Fourmigué, J.-C. P. Gabriel, . 1998, , 3005. 1986, L. Brossard, M. Ribault, M. Bousseau, L. Valade, P. Cassoux, , 205. R. Kato, . 2004, , 5319. 1991, K. Tanigaki, T. W. Ebbesen, S. Saito, J. Mizuki, J. S. Tsai, Y. Kubo, S. Kuroshima, , 222. A. Y. Ganin, Y. Takabayashi, Y. Z. Khimyak, S. Margadonna, A. Tamai, M. J. Rosseinsky, K. Prassides, . 2008, , 367. c, D. Aržcon, T. Takano, Y. Iwasa, Y. Ohishi, M. Takata, N. Takeshita, K. Prassides, M. Y. Takabayashi, A. Y. Ganin, P. Jegliž 2009, J. Rosseinsky, , 1585. R. Mitsuhashi, Y. Suzuki, Y. Yamanari, H. Mitamura, T. Kambe, N. Ikeda, H. Okamoto, A. Fujiwara, M. Yamaji, N. 2010, Kawasaki, Y. Maniwa, Y. Kubozono, , 76. X. F. Wang, R. H. Liu, Z. Gui, Y. L. Xie, Y. J. Yan, J. J. Ying, X. G. Luo, X. H. Chen, . 2011, , 1513. Y. Kubozono, H. Mitamura, X. Lee, X. He, Y. Yamanari, Y. Takahashi, Y. Suzuki, Y. Kaji, R. Eguchi, K. Akaike, T. Kambe, H. Okamoto, A. Fujiwara, T. Kato, T. Kosugi, H. Aoki, . 2011, , 16476. M. Xue, T. Cao, D. Wang, Y. Wu, H. Yang, X. Dong, J. He, F. Li, G. F. Chen, . 2012, , srep00389.

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

229

Materials Chemistry

1) 2) 3) 4) 5) 6) 7) 8) 9) 10) 11)

Materials Chemistry

Synthetic Organic Chemistry

Building Blocks for Semiconducting Polymer

Building Blocks for Semiconducting Polymer Polyacetylenes exhibit semiconducting-insulating properties by a lack of free electrons (carriers), although there are conducting pathways through π-conjugations. Shirakawa, MacDiarmid and Heeger . in 1977 observed that polyacetylenes show high electrical conduction comparable with a metal when the insulating polyacetylenes obtain carriers by a bromine doping.1) After their observation, studies of conducting polymers were dramatically enhanced, and some of the representative polymers were practical for electronic equipment. In 1990s, an organic light-emitting diode (OLED) of polyphenylene vinylene (PPV) was reported and then semiconducting polymers attracted us in this research area.2) The PPV is one of the light-emitting polymers (LEP) and the functionality is due to the semiconducting property of a π-conjugated polymer without a chemical doping. A chemical modification of a π-conjugated polymer can create various colored emissions. For instance, polyfluorenes (PFO),3) PPVs4) and regiorandom poly(3-octylthiophene) (P3OT)5) exhibit blue, green and red emissions, respectively. C8H17

C8H17

C8H17

n

n

PPV

PFO

S

n

P3OT

Recent research on organic electronics developed sulfur-containing polymers such as polythiophene. Poly(3,4-ethylenedioxythiophene) (PEDOT) is useful for a capacitor, organic transistor, hole transport material for an OLED device, and secondary battery as well as for an actuator, sensor and thermoelectric conversion element.6,7) PEDOT/PSS that is mixture of PEDOT and polystyrene sulfonate (PSS), is widely used as a hole transport material for organic photovoltaics (OPV).8) Poly(3-hexyl)thiophene (P3HT) can be blended with fullerene derivatives (eg. PCBM) to form an efficient bulk heterojunction. The polymer for the OPV device works as a p-type semiconductor with light absorption.9) O

C6H13

O

S PEDOT

n

S

n

P3HT [P2018]

On the other hand, some thiophene-based polymers exhibit a high energy level of the highest occupied molecular orbital (HOMO), because they are electron-rich. One problem of the thiophene-based polymers is their sensitivity for electrochemical oxidation. In order to solve the problem, one can combine an electron-rich monomer (donor) and an electron-deficient monomer (acceptor) to decrease the HOMO energy level and then stable donor-acceptor (DA type) polymers can be produced.10-12) The DA type polymer usually shows a low band gap state which can absorb light of long wavelength. Furthermore, several DA type polymers are ambipolar enabling both p- and n-dopes.13,14)

230

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Building Blocks for Semiconducting Polymer

Synthetic Organic Chemistry

Low Band Gap Polymers

O

O

F

N

S S

Donor S

S

n

n

S

Acceptor

Donor

C8H17

C8H17

O

S

N

Donor O

S

Donor

N

Acceptor PCDTBT

PTB7

Materials Chemistry

B4685

B4102 CH3 CH3

Donor Raw Materials

H3C H3C Sn H3C

Thiophenes

CH3

CH3

O S CH3 Sn CH3 CH3

S O

CH3

CH3 S

CH3

S

CH3

B4437

B4378 CH3 S

CH3

CH3 CH3

CH3 S Sn

CH3 CH3

H3C H3C Sn

S

S

B4585

Br

S

O

CH3

O

B

Sn CH3

S

CH3

O

CH3

H3C Sn

(CH2)11CH3

S

H 3C

CH3 S

CH3

B4584

Sn CH3

D3954 (CH2)7CH3

I

S

Br

Br

D4568 CH3

S

CH3

CH3

I

Br

S

I

D3941

Br

S

Br

Si(CH3)3

CH3 S

Br

S

D4572

Br

(CH2)9CH3

S

S

Br

S

S

Br

Br

Br

S

Br

CH3(CH2)7O

D2245

Br

Br S

S

Br

D2755

Br

S (CH3)3Si

S

D3798

O(CH2)7CH3

S

O B

S

CH3

(CH2)5CH3

CH3

D4621 Br

B4586

CH3

B3865

CH3 I

CH3

O(CH2)7CH3 CH3

CH3

CH3

CH3

CH3

CH3

B4536 H 3C

O(CH2)7CH3 S

H3C

Sn CH3 S

B3363

D4274

D4183

D4184

D3799

(CH2)5CH3 Br

Br Br S

Br

S

S

Br CH3(CH2)5

S

Br

CH3(CH2)5 Br

(CH2)5CH3 S

S

Br

Br

S

S

Br

S

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

231

Building Blocks for Semiconducting Polymer

Synthetic Organic Chemistry

D3800 S

D4056

D3896

(CH2)11CH3

S

Br

S

Br

D4053

Br

O

Br

S

Br

D4050

(CH2)5CH3 Br

Br

S

D4032

S

Br

D3679

232

S

S

D4582 S

Br

S

Br

S

O

S

S

Br

S

Br

CH3(CH2)7

Si

S N

(CH2)7CH3

S

Br S

Br

Br

S

S

O

O

E0743

O

O O

(CH2)7CH3

Br

S

D4033

E0741

C OH

Br

Br

Br

S

D4564

Br S

Br

S

D3678 Br

Br

D4714

O

(CH2)7CH3 Br

Materials Chemistry

D4031

S

HO C

Product No.

Product Name

B4685 B4102 B4437 B4378 B3363 B4536 B4586 B4585 B3865 B4584 D3954 D4568 D4621 D3941 D3798 D2755 D4572 D2245 D4274 D4183 D4184 D3799 D3800 D4031 D4056 D3896 D4714 D4053 D4050 D4032 D3678 D4033 D3679 D4582 D4564 E0741 E0743

4,8-Bis(2-butyl-n-octyloxy)-2,6-bis(trimethylstannyl)benzo[1,2-b:4,5-b ']dithiophene 4,4-Bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b ']dithiophene 4,8-Bis[5-(2-ethylhexyl)thiophen-2-yl]-2,6-bis(trimethylstannyl)benzo[1,2-b:4,5-b ']dithiophene 4,8-Bis(n-octyloxy)-2,6-bis(trimethylstannyl)benzo[1,2-b:4,5-b ']dithiophene 5,5'-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,2'-bithiophene 2,5-Bis(trimethylstannyl)thieno[3,2-b]thiophene 2-Bromo-3-dodecyl-5-iodothiophene (stabilized with Copper chip) 2-Bromo-3-(2-ethylhexyl)-5-iodothiophene (stabilized with Copper chip) 2-Bromo-3-hexyl-5-iodothiophene (stabilized with Copper chip) 2-Bromo-5-iodo-3-n-octylthiophene (stabilized with Copper chip) 2,6-Dibromobenzo[1,2-b:4,5-b ']dithiophene 2,6-Dibromo-4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b ']dithiophene 2,6-Dibromo-4,8-bis(n-octyloxy)benzo[1,2-b:4,5-b ']dithiophene 3,3'-Dibromo-5,5'-bis(trimethylsilyl)-2,2'-bithiophene 3,3'-Dibromo-2,2'-bithiophene 1g 5,5'-Dibromo-2,2'-bithiophene 2,5-Dibromo-3-decylthiophene 2,8-Dibromodibenzothiophene 1g 3,7-Dibromodibenzo[b,d]thiophene 5,5'-Dibromo-3,3'-dihexyl-2,2'-bithiophene 5,5'-Dibromo-4,4'-dihexyl-2,2'-bithiophene 2,6-Dibromodithieno[3,2-b:2',3'-d]thiophene 3,5-Dibromodithieno[3,2-b:2',3'-d]thiophene 2,5-Dibromo-3-dodecylthiophene 2,5-Dibromo-3,4-ethylenedioxythiophene 2,5-Dibromo-3-hexylthiophene 2,6-Dibromo-4-n-octyldithieno[3,2-b:2',3'-d]pyrrole 2,5-Dibromo-3-n-octylthiophene 5,5''-Dibromo-2,2':5',2''-terthiophene 2,5-Dibromothieno[2,3-b]thiophene 200mg 2,5-Dibromothieno[3,2-b]thiophene 3,4-Dibromothieno[2,3-b]thiophene 3,6-Dibromothieno[3,2-b]thiophene 2,5-Dibromothiophene-3-carboxylic Acid 4,4-Di-n-octyldithieno[3,2-b:2,3-d ']silole 3,4-Ethylenedioxythiophene 3,4-Ethylenedioxythiophene-2,5-dicarboxylic Acid

O S

C OH

Unit Size 1g

200mg 1g 1g 1g

1g 5g 1g 5g 5g 1g 200mg 200mg 200mg 1g 5g

1g 1g 200mg 1g 5g 1g

200mg 5g 200mg 200mg 5g 1g 1g 5g 5g 1g 5g 200mg 200mg 5g 25g 5g 25g 25g 200mg 5g 1g 1g 1g 5g 5g 25g 200mg 5g 5g 1g 5g 1g 1g 5g 200mg 25g 5g

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Building Blocks for Semiconducting Polymer

A2051

B2805 O

I

Carbazoles

C H

N

Br

C CH3

N

N CH2

CH2

Br

D2983

D2982

Br

Br

D4735

Br

N H

Br

N

Br

N

N H

D4482

D4548

Br Br

N

Br

I I

I

I

O0439

CH3

CH3

CH3

CH3

O

O B

O CH3 CH3(CH2)7

N H

(CH2)7CH3

O0428

CH3

N

N

(CH2)7CH3

(CH2)7CH3

D4543

Br N

Br

Br

N

CH3(CH2)7

CH3

D2981

Br

Br CH3

CH2CH3

Materials Chemistry

D3935

D4490

Br Br

Br

Br

Br

N

O

D3932

Br

O

H C

D4563

Synthetic Organic Chemistry

I

B4348

CH3

CH3

B O

(CH2)7CH3

CH3 O

O

B

N

CH3

CH3

CH3

O CH3

CH3

B

N

O

(CH2)7CH3

CH3 CH3

Product No.

Product Name

A2051 B2805 B4348 D4563 D3932 D2983 D2982 D4735 D4490 D3935 D4482 D2981 D4548 D4543 O0428 O0439

9-Acetyl-3,6-diiodocarbazole 9-Benzylcarbazole-3,6-dicarboxaldehyde 9-Benzyl-3,6-dibromocarbazole 3,6-Dibromo-9-(4-bromophenyl)carbazole 2,7-Dibromocarbazole 3,6-Dibromocarbazole 3,6-Dibromo-9-ethylcarbazole 2,7-Dibromo-9-(2-ethylhexyl)carbazole 2,7-Dibromo-9-(9-heptadecyl)carbazole 2,7-Dibromo-9-n-octylcarbazole 3,6-Dibromo-9-n-octylcarbazole 3,6-Dibromo-9-phenylcarbazole 3,6-Diiodocarbazole 3,6-Diiodo-9-phenylcarbazole 9-(9-Heptadecanyl)-2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)carbazole 9-n-Octyl-2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)carbazole

Unit Size

B4588

Fluorenes

CH3 CH3

CH3 O B OCH (CH ) 3 2 9 CH3

B4624

O B (CH2)9CH3O

CH3

CH3

CH3

CH3

O CH3(CH2)11 CH3

200mg 200mg 1g 5g 1g 200mg

CH3

B (CH2)11CH3 O

CH3 CH3

CH3

O

CH3

O CH3(CH2)5

B CH3

5g 100mg 1g 1g 5g 25g 5g 200mg 1g 200mg 1g 5g 25g 5g 1g 200mg

B3582

CH3

CH3 O

O B

200mg 1g 1g 5g 1g

B4029

CH3

CH3 CH3

1g

O B (CH2)5CH3 O

CH3 CH3 CH3 CH3

CH3 CH3

CH3

CH3 O

O B

O CH3(CH2)7

CH3

B (CH2)7CH3 O

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

CH3 CH3 CH3

233

Building Blocks for Semiconducting Polymer

Synthetic Organic Chemistry

D4719

H2N CH3(CH2)7

NH2 (CH2)7CH3

Br

Br(CH2)6

D4550

(CH2)6Br

Br

D4561

Br CH3

Br CH3 N

N

CH3

D3859

Br

Materials Chemistry

B3552

D3934

CH3

CH3

Br

D3781

Br CH3(CH2)7

D4504

Br

Br (CH2)9CH3

D3556

Br

Br (CH2)5CH3

D3557

Br Br CH3

Br

Br

Br O

CH3

O

I

H C CH3(CH2)7

O C H (CH2)7CH3

Product No.

Product Name

B4588 B4624 B4029 B3582 D4719 B3552 D4550 D4561 D3933 D3859 D3934 D4569 D3556 D3557 D3781 D4504 D4671

2,7-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-didecylfluorene 2,7-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-didodecylfluorene 2,7-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-dihexylfluorene 2,7-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-di-n-octylfluorene 2,7-Diamino-9,9-di-n-octylfluorene 2,7-Dibromo-9,9-bis(6-bromohexyl)fluorene 2,7-Dibromo-9,9-bis[3-(dimethylamino)propyl]fluorene 2,7-Dibromo-9,9-didecylfluorene 2,7-Dibromo-9,9-dihexylfluorene 2,7-Dibromo-9,9-dimethylfluorene 2,7-Dibromo-9,9-di-n-octylfluorene 2,7-Dibromo-9,9-dipropylfluorene 2,7-Dibromofluorene 2,7-Dibromo-9-fluorenone 2,7-Dibromo-9,9'-spirobi[9H-fluorene] 2,7-Diiodofluorene 9,9-Di-n-octylfluorene-2,7-dicarboxaldehyde

Unit Size

200mg 1g 200mg 5g 5g 5g 5g 1g 5g 25g 5g 1g

D4219 Br

Acceptor Raw Materials

Br CH3(CH2)5

D4671

Br I

Br CH3(CH2)9

CH3

D4569

Br (CH2)7CH3

D3933

Thiophenes

S

E1040 O N

Br

(CH2)7CH3

O

F

CH3

S Br

Br

1g 1g 1g 1g 1g 5g 1g 25g 25g 25g 25g 5g 100g 25g 1g 5g 1g

O

S

CH3

O

O0436 Br F S Br

234

O(CH2)7CH3

S O

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Building Blocks for Semiconducting Polymer

Product Name

D4219 E1040 O0436

2,5-Dibromo-N-n-octyl-3,4-thiophenedicarboximide 2-Ethylhexyl 4,6-Dibromo-3-fluorothieno[3,4-b]thiophene-2-carboxylate n-Octyl 4,6-Dibromo-3-fluorothieno[3,4-b]thiophene-2-carboxylate

Unit Size

B3573

D3842 CH3

N

Benzothiadiazoles

N O CH3

D4734 Br

Br CH3(CH2)11O

N

Br N

N

O

F

N

S

N

CH3(CH2)11O

Br

Br

Br

CH3 CH3 CH3

N

S

S

S

F

D4750 Br

Br CH3(CH2)7O

F

N

N S

S N

N

CH3(CH2)7O

Materials Chemistry

D4529

B

200mg 100mg 100mg

D4622

CH3 CH3 CH3 O O B

Synthetic Organic Chemistry

Product No.

Br

Br

Product No.

Product Name

B3573 D3842 D4622 D4734 D4529 D4750

4,7-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,1,3-benzothiadiazole 4,7-Dibromo-2,1,3-benzothiadiazole 4,7-Dibromo-5,6-bis(dodecyloxy)-2,1,3-benzothiadiazole 4,7-Dibromo-5,6-difluoro-2,1,3-benzothiadiazole 4,7-Dibromo-5,6-di-n-octyloxy-2,1,3-benzothiadiazole 4,7-Dibromo-5-fluoro-2,1,3-benzothiadiazole

Unit Size

D3944

D4653

D4514 OCH3

Br

Br

Others

Br N

N

D4461 Br

OCH3

D3209 O

Br

N

Br

Br

N S

N Br O

S

Br

Br

Br O

S

D4442

N N

Br

(CH2)8CH3

N N

Br

O

N

(CH2)6Br

N

N Br

D4339 O

CH3(CH2)8

N

Se Br

5g

D4558

N

N

1g 25g 200mg 200mg 200mg 200mg 1g

1g

O

Product No.

Product Name

D3944 D4653 D4514 D4558 D4461 D4339

4,7-Dibromo-2,1,3-benzoselenadiazole 5,8-Dibromo-2,3-bis(4-methoxyphenyl)quinoxaline 4,7-Dibromo-2-(6-bromohexyl)benzotriazole 5,5'-Dibromo-4,4'-dinonyl-2,2'-bithiazole 5,8-Dibromo-2,3-diphenylquinoxaline 2,6-Dibromonaphthalene-1,4,5,8-tetracarboxylic Dianhydride

N Br

Unit Size 1g 200mg 200mg 200mg 200mg 1g 5g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

235

Synthetic Organic Chemistry

Building Blocks for Semiconducting Polymer

Product No.

Product Name

D3209 D4442

3,8-Dibromo-1,10-phenanthroline 4,7-Dibromo[1,2,5]thiadiazolo[3,4-c]pyridine

Unit Size 200mg 200mg

B4719

B3886

1g 1g

B4419 (CH2)7CH3

CH3(CH2)11

DA-Type Monomers

O

(CH2)11CH3

Br

S

S N

S

Br

Br

S

S

N

N

S

N

N S

Br Br

Br

S N

O

Materials Chemistry

(CH2)7CH3

B4453

D4487

D3969 O

(CH3)3Sn

S

S N

S

Sn(CH3)3

S

H N S

S

N

N

S

S

N

N H

O

Product No.

Product Name

B4719 B3886 B4419 B4453 D4487 D3969

4,7-Bis(5-bromo-4-dodecyl-2-thienyl)-2,1,3-benzothiadiazole 4,7-Bis(5-bromo-2-thienyl)-2,1,3-benzothiadiazole 3,6-Bis(5-bromo-2-thienyl)-2,5-di-n-octylpyrrolo[3,4-c]pyrrole-1,4-dione 4,7-Bis(5-trimethylstannyl-2-thienyl)-2,1,3-benzothiadiazole 4,7-Di(2-thienyl)-2,1,3-benzothiadiazole 3,6-Di(2-thienyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione

Unit Size

B1458

200mg 1g 200mg 200mg 200mg 1g 1g 5g 100mg

D2098

D4180 (CH2)5CH3

(CH2)3CH3

Raw Materials for Oxidative Polymerization, Thiophenes

D3928

(CH2)9CH3

S

S S

D4182

S

D4202

CH3(CH2)5

D2016

E0741

CH3(CH2)5 S

S

CH3(CH2)5

(CH2)5CH3 S

CH3(CH2)5

S

(CH2)11CH3

(CH2)5CH3 S

O

S

S

CH3(CH2)5

E0973

H0722

H1350

S

236

CH3

H0756

N0533 (CH2)5CH3

(CH2)6CH3

CH3 S

S

(CH2)5CH3

O

S

(CH2)8CH3 S

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Building Blocks for Semiconducting Polymer

O0245

O0383

O0376

O0213 (CH2)7CH3

CH3(CH2)7

S

P1127

Synthetic Organic Chemistry

(CH2)17CH3

P1835

S

S

S

(CH2)7CH3

S

S

(CH2)4CH3

U0056 (CH2)10CH3

(CH2)4CH3 S

S

Product Name

B1458 D2098 D4180 D3928 D4182 D4202 D2016 E0741 E0973 H0722 H1350 H0756 N0533 O0245 O0383 O0376 O0213 P1835 P1127 U0056

3-Butylthiophene 3-Decylthiophene 3,3'-Dihexyl-2,2'-bithiophene 3,4'-Dihexyl-2,2'-bithiophene 4,4'-Dihexyl-2,2'-bithiophene 3,4-Dihexylthiophene 3-Dodecylthiophene 3,4-Ethylenedioxythiophene 3-(2-Ethylhexyl)thiophene 3-Heptylthiophene 2-Hexylthiophene 3-Hexylthiophene 3-Nonylthiophene 3-Octadecylthiophene 5-n-Octyl-2,2'-bithiophene 2-n-Octylthiophene 3-n-Octylthiophene 2-Pentylthiophene 3-Pentylthiophene 3-Undecylthiophene

Materials Chemistry

Product No.

Unit Size 1g 1g 1g 1g 200mg 1g 1g 5g 5g 200mg 1g 5g 1g 5g 1g 1g

1g

5g 1g 1g

5g 5g 5g 5g 1g 5g 25g 25g 1g 5g 25g 25g 5g 5g 1g 5g 25g 5g 5g 5g

References 1) H. Shirakawa, E. J. Louis, A. G. MacDiarmid, C. K. Chiang, A. J. Heeger, . 1977, 578. 2) J. H. Burroughes, D. D. C. Bradley, A. R. Brown, R. N. Marks, K. Mackay, R. H. Friend, P. L. Burns, A. B. Holmes, 1990, , 539. 3) A. W. Grice, D. D. C. Bradley, M. T. Bernius, M. Inbasekaran, W. W. Wu, E. P. Woo, . 1998, , 629. 4) Review: A. B. Holmes, D. D. C. Bradley, A. R. Brown, P. L. Burn, J. H. Burroughes, R. H. Friend, N. C. Greenham, R. W. Gymer, D. A. Halliday, R. W. Jackson, A. Kraft, J. H. F. Martens, K. Pichler, I. D. W. Samuel, . 1993, , 4031. 5) D. Braun, G. Gustafsson, D. McBranch, A. J. Heeger, . 1992, , 564. 6) Review: L. Groenendaal, F. Jonas, D. Freitag, H. Pielartzik, J. R. Reynolds, . 2000, , 481. 7) A. Elschner, S. Kirchmeyer, W. Lovenich, U. Merker, K. Reuter, in , CRC Press, 2010. 8) Review: C. Winder, N. S. Sariciftci, . 2004, , 1077. 9) Review: M. T. Dang, L. Hirsch, G. Wantz, . 2011, , 3597. 10) Y. Liang, Z. Xu, J. Xia, S.-T. Tsai, Y. Wu, G. Li, C. Ray, L. Yu, . 2010, , E135. 11) N. Blouin, A. Michaud, M. Leclerc, . 2007, , 2295. 12) P. M. Beaujuge, W. Pisula, H. N. Tsao, S. Ellinger, K. Müllen, J. R. Reynolds, . 2009, , 7514. 2013, , 051601. 13) H. Ito, T. Iwata, S. Watanabe, S. Kuroda, 14) S. Cho, J. H. Seo, G.-H. Kim, J. Y. Kim, H. Y. Woo, . 2012, , 21238.

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

237

Building Blocks for Small Molecule Semiconductor Several features of small molecule organic semiconductors are that they are isolable in a chemically pure form, it is possible to determine structures by a single crystal structure analysis, it is possible to fabricate a thin-layer and to purify it by vacuum deposition. In comparison with inorganic materials, organic materials are structurally diverse based on the carbon-centered geometry. Therefore, we can precisely control physical properties such as photo absorption, emission properties, energy level and solubility by applying organic synthesis. Several conventional coupling reactions can enable expansion of π-conjugated structures. In particular, palladium- and copper-catalyzed cross-coupling reactions can systematically and rapidly produce various organic compounds to develop new materials. The following lists plenty of‘Building Blocks for Small Molecule Semiconductors’bearing halogen, boronic acid (ester), a stannyl group, amino group, or formyl group. B3793

Materials Chemistry

Synthetic Organic Chemistry

Building Blocks for Small Molecule Semiconductor

B4774

B3777

O B(OH)2

S

O

Thiophenes

C H

S

S

S O

B4086

B2033

B2893

B1838

B3762

O C H S

S

B1874

Br

S

S

B3525

S

S

Br

B3738

B3691 (CH2)11CH3

B3812

B3733

CH3(CH2)5

(CH2)7CH3 CH3(CH2)5

Br

S

B4050

Br

S

B2058

S

Br

S

CH3

B3692

S

Br

S

S

B4126 S

238

Br

B3226

S

O

S

Br S

Br

S

S

S

O

O

CH3

O

B

S

S

C2457 (CH2)5CH3

C H S

C H

CH3

CH3

C2613

Br

Br

S

B3200

Br CH3(CH2)7

Br

S

Br

Br

B3663

S

S

B3985

S

C H

B4449

S

(CH2)5CH3

CH3

S

Br

Br

B3507

CH3

S

B(OH)2

(CH2)3CH3

C H

B4783

S

C OH

B4511

O

Br

O

O

S

Cl

Cl

CH3 S

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Br

Building Blocks for Small Molecule Semiconductor

C3021

C2715

D4373

D4057

S

S

D4767

O

B(OH)2

S

C H S

S

S

D4822

B(OH)2

D3823

D4290

S

D4291

CH3(CH2)11 CH3

S S

S

C H

Br

O

H1294

CH3(CH2)5 CH3 H C

S

S

B(OH)2

O

CH3

CH3

O

CH3

B

S

B O

O

CH3

O

N

CH3

T2772 Br

S

Br

(CH2)7CH3

O

S

T2699

O S

S

S

C H

T2621

S

Br

O

S

S

Br

T3221

S B

CH3

CH3

O CH3

CH3

T3156

I

Br

S

O

CH3

S

CN

Br

T3236

B

S

CH3(CH2)5 S

CH3 CH3

I0947

O

T2518

S

O CH3

O S

S

CH3

T1805

(CH2)7CH3 B

(CH2)11CH3

O B

CH3

CH3

CH3

CH3

S

O

S

O0394

CH3

CH3

Br

(CH2)5CH3

O

CH3

CH3

O

CH3

Br

CH3

S

O0411

CH3(CH2)7

CH3

CH3

B

H1503

CH3

B O

CH3

O0410

B(OH)2

CH3

H1298

O

S

O

Materials Chemistry

F0548

S

Br

Synthetic Organic Chemistry

O

D4777

S S

B(OH)2

S

CN

CH3

T2897 O

S O S

S

O

C OH O

Product No.

Product Name

B3793 B4774 B3777 B4086 B2033 B2893 B1838 B3762 B1874 B4511 B3525 B4449 B3691 B4783

Benzo[1,2-b:4,5-b ']dithiophene-4,8-dione Benzo[b]thiophene-3-boronic Acid (contains varying amounts of Anhydride) Benzo[b]thiophene-2-carboxaldehyde Benzo[b]thiophene-3-carboxaldehyde Benzo[b]thiophene-2-carboxylic Acid Benzo[b]thiophene-2-ylboronic Acid (contains varying amounts of Anhydride) 2,2'-Bithiophene-5-carboxaldehyde 5-Bromobenzo[b]thiophene 5-Bromo-2,2'-bithiophene-5'-carboxaldehyde 2-Bromo-3-butylthiophene 2-Bromodibenzothiophene 4-Bromodibenzothiophene 2-Bromo-3-dodecylthiophene 2-Bromo-3-(2-ethylhexyl)thiophene

Unit Size 1g 1g 1g 1g 1g

5g 5g 1g 1g 5g 5g 1g 1g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

5g 5g 5g 5g 1g 25g 25g 5g 5g 25g 25g 5g 5g 5g

239

Materials Chemistry

Synthetic Organic Chemistry

Building Blocks for Small Molecule Semiconductor

Product No.

Product Name

B3507 B3985 B3812 B3733 B3738 B3663 B4050 B2058 B3200 B3692 B3226 B4126 C2613 C2457 C3021 C2715 D4373 D4057 D4777 D4767 D4822 D3823 D4290 D4291 F0548 H1298 H1294 H1503 I0947 O0410 O0411 O0394 T1805 T2699 T2772 T2518 T3236 T2621 T3221 T3156 T2897

2-Bromo-3-hexylthiophene 2-Bromo-4-hexylthiophene 2-Bromo-5-hexylthiophene 2-Bromo-3-n-octylthiophene 2-Bromo-5-n-octylthiophene 2-Bromo-5-phenylthiophene 3'-Bromo-2,2':5',2''-terthiophene 5''-Bromo-2,2':5',2''-terthiophene-5-carboxaldehyde 5-Bromo-5'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,2'-bithiophene 2-Bromothieno[2,3-b]thiophene 3-Bromothieno[3,2-b]thiophene 4-Bromothiophene-3-carboxaldehyde 2-Chloro-3-hexylthiophene 5-Chloro-3-methylbenzo[b]thiophene 4H-Cyclopenta[2,1-b:3,4-b ']dithiophene 4H-Cyclopenta[1,2-b:5,4-b ']dithiophen-4-one Dibenzothiophene-2-boronic Acid (contains varying amounts of Anhydride) Dibenzothiophene-4-boronic Acid (contains varying amounts of Anhydride) Dibenzothiophene-2-carboxaldehyde Dibenzothiophene-4-carboxaldehyde 4,6-Dibromodibenzothiophene Dithieno[3,2-b:2',3'-d]thiophene-2-boronic Acid (contains varying amounts of Anhydride) 3-Dodecyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene 4-Dodecyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene 5'-Formyl-2,2'-bithiophene-5-boronic Acid (contains varying amounts of Anhydride) 3-Hexyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene 4-Hexyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene 4-Hexylthiophene-2-carbonitrile 4-Iododibenzothiophene 3-n-Octyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene 4-n-Octyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene N-n-Octyl-3,4-thiophenedicarboximide 2,2':5',2''-Terthiophene-5-carboxaldehyde 3,3',5,5'-Tetrabromo-2,2'-bithiophene 2,3,5,6-Tetrabromothieno[3,2-b]thiophene 5-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-2,2'-bithiophene 4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)dibenzothiophene Thieno[3,2-b]thiophene-2-boronic Acid (contains varying amounts of Anhydride) Thieno[3,2-b]thiophene-2-carbonitrile Thieno[3,2-b]thiophene-2-carboxylic Acid 3,4-Thiophenedicarboxylic Anhydride

Unit Size

A2051

B4348

H C

C H

B4646

Br N

1g

5g

1g

5g 1g 200mg 200mg

C H

N

N

CH2CH3

CH2

B4816

B3458

B4752

N H

N H

N

N H

B4795

Br

Br N

N H

Br

B3459

Br

Br

240

1g 1g 1g 200mg

B4538

N H

CH2

Br

5g

Br

CH2

N H

1g

Br

N

B4381

1g 1g 1g 1g 200mg 200mg 1g 1g

NH2

O

O

5g 200mg

O

I

C CH3

O

200mg 200mg

25g 1g 5g 5g 25g 5g 5g 5g 1g 1g 1g 1g 5g 25g 1g 200mg 5g 5g 5g 5g 1g 1g 5g 5g 1g 25g 5g 200mg 5g 5g 5g 1g 1g 25g 1g 25g 5g 1g 1g 1g 1g

B2804

N

B2805

5g 1g 1g 1g

100mg

A1508

I

Carbazoles

5g

N CH2CH3

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Building Blocks for Small Molecule Semiconductor

B4439

B3908

B3554

B4452

C0032

N

Br

Synthetic Organic Chemistry

Br

Br N

N

N

N H

Br

C1031

C2967

C2926

D2116 H2N

N

N

N

D4473 NH2 N H

C Cl O

B(OH)2

D3932

Br

D2983

D2982

D2981

Br

Br Br

N

Br

Br

Materials Chemistry

D4563

N H

B(OH)2

Br

Br N

Br

N H

Br

N

N H

CH2CH3

Br

D3952

D3751

D4275

D4548

D4543 I

H3C

CH3

H3C C

Cl

Cl

C CH3

H3C

CH3

C CH

D4433

I

I N

N H

N H

N H

D4512

HC C

I N H

E0359

E0972

E1055

O CH3

CH3

C H

N H

CH3

N

N H

F0965

CH2CH3

H1014

CH3

I0913

I0961

M2561 CH3

N

N N H

C CH

I

OH

F

N

N

N H

N H I

N1012

P2169

P2001

T2932

V0021

B(OH)2 Br N

N

B(OH)2

Br

N Br

Product No.

Product Name

A2051 A1508 B2804 B2805 B4348 B4646

9-Acetyl-3,6-diiodocarbazole 3-Amino-9-ethylcarbazole 9-Benzylcarbazole-3-carboxaldehyde 9-Benzylcarbazole-3,6-dicarboxaldehyde 9-Benzyl-3,6-dibromocarbazole 3,3'-Bicarbazole

N H

N Br

CH

CH2

Unit Size 1g

5g 5g 1g 5g 100mg 1g 200mg 1g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

241

Materials Chemistry

Synthetic Organic Chemistry

Building Blocks for Small Molecule Semiconductor

Product No.

Product Name

B4538 B4816 B4381 B3458 B4752 B4795 B3459 B4439 B3908 B3554 B4452 C0032 C1031 C2967 C2926 D2116 D4473 D4563 D3932 D2983 D2982 D2981 D3952 D3751 D4275 D4548 D4543 D4512 D4433 E0359 E0972 E1055 F0965 H1014 I0913 I0961 M2561 N1012 P2169 P2001 T2932 V0021

9-(4-Biphenylyl)-3-bromocarbazole 1-Bromocarbazole 2-Bromocarbazole 3-Bromocarbazole 4-Bromocarbazole 3-Bromo-6,9-diphenylcarbazole 3-Bromo-9-ethylcarbazole 2-Bromo-9-phenylcarbazole 3-Bromo-9-phenylcarbazole 9-(4-Bromophenyl)carbazole 3-(4-Bromophenyl)-9-phenylcarbazole Carbazole Carbazole-9-carbonyl Chloride 3-(9H-Carbazol-9-yl)phenylboronic Acid (contains varying amounts of Anhydride) 4-(9H-Carbazol-9-yl)phenylboronic Acid (contains varying amounts of Anhydride) 3,6-Diaminocarbazole 7H-Dibenzo[c,g]carbazole 3,6-Dibromo-9-(4-bromophenyl)carbazole 2,7-Dibromocarbazole 3,6-Dibromocarbazole 3,6-Dibromo-9-ethylcarbazole 3,6-Dibromo-9-phenylcarbazole 3,6-Di-tert-butylcarbazole 3,6-Dichlorocarbazole 3,6-Diethynylcarbazole 3,6-Diiodocarbazole 3,6-Diiodo-9-phenylcarbazole 3,6-Dimethylcarbazole 3,6-Diphenylcarbazole N-Ethylcarbazole-3-carboxaldehyde 9-(2-Ethylhexyl)carbazole 9-(4-Ethynylphenyl)carbazole 3-Fluorocarbazole 4-Hydroxycarbazole 3-Iodo-9-phenylcarbazole 9-(4-Iodophenyl)carbazole 3-Methyl-9H-carbazole 9-(1-Naphthyl)carbazole 9-Phenylcarbazole-2-boronic Acid (contains varying amounts of Anhydride) 9-Phenylcarbazole-3-boronic Acid (contains varying amounts of Anhydride) 1,3,6,8-Tetrabromocarbazole 9-Vinylcarbazole

Unit Size

A2634

A1040

B3931

B0059

200mg 1g 1g 1g 1g 1g 1g 25g 100g 1g 5g 1g 1g 1g 200mg 1g 1g 5g 1g 1g 1g 1g 200mg 5g 1g 1g 1g 1g 1g

CH3

5g 1g 1g 1g 200mg 5g 200mg

A2779

Fluorenes & Fluorenones CH3

5g 200mg

25g 1g 5g 5g 1g 5g 5g 5g 5g 5g 5g 500g 25g 5g 5g 5g 200mg 1g 5g 25g 5g 5g 5g 5g 1g 25g 5g 1g 5g 25g 5g 5g 1g 25g 5g 5g 1g 5g 1g 25g 1g 25g

A0621

NH2

NH2

NH2

B3933

B3932

NH2 O

242

O

O

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Building Blocks for Small Molecule Semiconductor

B4441

B3894

B4661

B4668

CH3(CH2)3

CH CH2

CH2

CH2CH3

Br CH (CH2)3CH3

CH3

CH2CH3

B4450

O

CH3

CH3

Br

Br

CH3

CH3

B4776

B3069

Br (CH2)7CH3

CH3(CH2)7

O

CH3

Synthetic Organic Chemistry

Br

B4366

B3109

B4431

Br

Br

Br

Br

B3560

D3557

D4573

D3872 O

Br

Br

Br

Br

Br

Br

Br

O

D4084

H3C H3C C H3C

D4327

Br

Br

O

D3974

Materials Chemistry

B1702

I

O

D3235

D3586

CH3 C CH3 CH3

F0017

CH3(CH2)5

(CH2)5CH3

F0021

CH3

S0800

B(OH)2

F0228

CH3

CH3

H0329

F

O

I0793

CH3

I0875

OH O

CH3

CH3

I

S0831

B(OH)2 I

Product No.

Product Name

A2634 A2779 A0621 A1040 B3931 B0059 B3933 B3932 B4441 B3894 B4661 B4668 B4366 B4450

2-Amino-9,9-dimethylfluorene 2-Amino-9,9-diphenylfluorene 2-Aminofluorene 2-Amino-9-fluorenone 1,2-Benzofluorene 2,3-Benzofluorene 11H-Benzo[a]fluoren-11-one 11H-Benzo[b]fluoren-11-one 2-Bromo-9,9-bis(2-ethylhexyl)fluorene 2-Bromo-9,9-dimethylfluorene 4-Bromo-9,9-dimethylfluorene 2-Bromo-13,13-dimethyl-6H-indeno[1,2-b]anthracene-6,11(13H)-dione 2-Bromo-9,9-di-n-octylfluorene 2-Bromo-9,9-diphenylfluorene

Unit Size 200mg 1g 5g 1g 200mg 100mg

5g 200mg

1g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

1g 5g 25g 5g 1g 1g 1g 5g 1g 25g 1g 1g 1g 5g

243

Materials Chemistry

Synthetic Organic Chemistry

Building Blocks for Small Molecule Semiconductor

Product No.

Product Name

B4776 B3069 B3109 B4431 B1702 B3560 D3557 D4573 D3872 D4084 D4327 D3974 D3235 D3586 F0017 F0021 F0228 H0329 I0875 I0793 S0800 S0831

4-Bromo-9,9-diphenylfluorene 2-Bromofluorene 2-Bromo-9-fluorenone 2-Bromo-7-iodofluorene 9-Bromo-9-phenylfluorene 2-Bromo-9,9'-spirobi[9H-fluorene] 2,7-Dibromo-9-fluorenone 2,8-Dibromoindeno[1,2-b]fluorene-6,12-dione 2,2'-Dibromo-9,9'-spirobi[9H-fluorene] 2,7-Di-tert-butylfluorene 9,9-Dihexylfluorene 9,9-Dimethylfluoren-2-boronic Acid (contains varying amounts of Anhydride) 9,9-Dimethylfluorene 9,9-Diphenylfluorene Fluorene 9-Fluorenone 2-Fluorofluorene 2-Hydroxy-9-fluorenone 2-Iodo-9,9-dimethylfluorene 2-Iodofluorene 9,9'-Spirobi[9H-fluorene] 9,9'-Spirobi[9H-fluorene]-2-boronic Acid

Unit Size

A1709

5g

1g 25g 5g 5g 5g 5g

5g 1g 1g 5g 25g 25g 5g 5g 5g 1g 1g

A1687

5g 100g 25g 25g 25g 5g 25g 1g 1g 25g 5g 5g 5g 25g 500g 500g 25g 1g 25g 25g 5g 5g

A1843

NH2

NH2

B(OH)2

Anthracenes & Anthraquinones

A2328

A0779 B(OH)2

A2664

A1220 O

O

C H

C OH

A1894 O

A1150

A0502

O

O

C OH

C OH

B0018 O

O

C H

A0690

B4569 O

OH Br

HO C H

O

O

B1327

B2109 CH2Cl

CH2Cl

Br

O

P1137

HO

OH

HO

OH

B2688

B2871 B0872

O

Br

B2616

B3475 B2615 C C

Br

Br

C C

B2689

B1603

B4321 Br

O Br

O

244

O

O

Br

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Building Blocks for Small Molecule Semiconductor

B3442

B4451

B4426

B3977

B4475

Synthetic Organic Chemistry

Br Br

Br

B0816

Br

C1962 O

Br

C1289

C1046

CH3

C C

C CH3

D3180

Cl

O

CH2Cl

Cl

H2N

CH3 NH2 O

C C

O

D4230 Br

D3171 Br

D0166

D3181 Br

Br

O

Materials Chemistry

D3183

Br

Br Br

Br

Br

D3182

D0327 O

D4151 Cl

D2980 I

Br

Br

I

O

M0156 O

O CH3

CH3

Br

CH3 Cl

O

N0929

P1984

O

O

T3276 B(OH)2 CH3

B(OH)2

CH3

O B

CH3

O CH3

Product No.

Product Name

A1709 A1687 A1843 A2328 A0779 A1220 A1150 A0690 A2664 A1894 A0502 B0018 B4569 B1327 B2109 P1137 B3475 B2615 B2616 B2871 B0872 B2688 B2689 B1603

1-Aminoanthracene 2-Aminoanthracene 2-Anthraceneboronic Acid (contains varying amounts of Anhydride) 9-Anthraceneboronic Acid (contains varying amounts of Anhydride) 9-Anthracenecarboxaldehyde 1-Anthracenecarboxylic Acid 2-Anthracenecarboxylic Acid 9-Anthracenecarboxylic Acid Anthracene-9,10-dicarboxaldehyde Anthraflavic Acid Anthraquinone 1,2-Benzanthraquinone 9-(4-Biphenylyl)-10-bromoanthracene 9,10-Bis(chloromethyl)anthracene 9,10-Bis(3,5-dihydroxyphenyl)anthracene 9,10-Bis(phenylethynyl)anthracene 1-Bromoanthracene (purified by sublimation) 1-Bromoanthracene 2-Bromoanthracene 9-Bromoanthracene 9-Bromoanthracene 1-Bromoanthraquinone 2-Bromoanthraquinone 7-Bromobenz[a]anthracene

Unit Size 250mg 1g 25g 1g 5g 1g 1g 25g 5g 1g 5g 100mg 1g 100mg 1g 5g 25g 5g 1g 1g 5g 1g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

1g 1g 1g 5g 100g 1g 5g 25g 5g 5g 500g 25g 5g 25g 1g 5g 1g 500mg 5g 100g 25g 5g 25g 5g

245

Materials Chemistry

Synthetic Organic Chemistry

Building Blocks for Small Molecule Semiconductor

Product No.

Product Name

B4321 B3442 B4451 B4426 B3977 B4475 B0816 C1962 C1289 C1046 D3180 D3183 D4230 D3171 D0166 D3181 D3182 D0327 D4151 D2980 M0156 N0929 P1984 T3276

2-Bromo-9,10-di(2-naphthyl)anthracene 2-Bromo-9,10-diphenylanthracene 9-Bromo-10-(1-naphthyl)anthracene 9-Bromo-10-(2-naphthyl)anthracene 9-Bromo-10-phenylanthracene 9-(4-Bromophenyl)-10-phenylanthracene 2-tert-Butylanthraquinone 2-Chloroanthracene 1-Chloro-9,10-bis(phenylethynyl)anthracene 9-Chloromethylanthracene 2,6-Diaminoanthraquinone 1,5-Dibromoanthracene 1,8-Dibromoanthracene 2,6-Dibromoanthracene 9,10-Dibromoanthracene 1,5-Dibromoanthraquinone 2,6-Dibromoanthraquinone 9,10-Dichloroanthracene 1,8-Diiodoanthracene 2,3-Dimethylanthraquinone 2-Methylanthraquinone 10-(2-Naphthyl)anthracene-9-boronic Acid (contains varying amounts of Anhydride) 10-Phenyl-9-anthraceneboronic Acid (contains varying amounts of Anhydride) 4,4,5,5-Tetramethyl-2-[4-(10-phenylanthracen-9-yl)phenyl]-1,3,2-dioxaborolane

Unit Size

A0632

1g

5g 1g 5g 5g 5g 1g 500g 1g 10g 25g 250g 1g 5g 5g 500g 1g 5g 10g 5g 5g 500g 1g 1g 1g

1g 1g 1g 200mg 25g 1g 5g 25g

1g

1g 1g 100g

25g

1g 1g 1g 1g 25g

200mg

A2180

B3956

NH2 CH3

Pyrenes

CH3

NH2

B3957

B1495 Br

B2807

C1637

CH3 O

O B

B

O CH3

O

CH3 CH3 CH3 CH3

D2167

Br

NH2

CH2Cl

H3C

NH2

H3C C

Br

H3C

D2160

D2168 NH2

D4187

D3167

H2N

D3169 Br

Br

NH2

Br Br

H3C H3C C

NH2

Br

H3C

E0939

N0419

Br

N0838

P1625

NO2

C CH

P1448 B(OH)2

O C H

NO2

P1687

P1221 O C OH

T2716 Br

CH2OH Br

Br

Br

246

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Building Blocks for Small Molecule Semiconductor

1-Aminopyrene 4-Aminopyrene 2,7-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrene 2-Bromo-7-tert-butylpyrene 1-Bromopyrene 4-Bromopyrene 1-Chloromethylpyrene 1,3-Diaminopyrene 1,6-Diaminopyrene 1,8-Diaminopyrene 1,3-Dibromo-7-tert-butylpyrene 1,6-Dibromopyrene 2,7-Dibromopyrene 1-Ethynylpyrene 1-Nitropyrene 4-Nitropyrene 1-Pyreneboronic Acid (contains varying amounts of Anhydride) 1-Pyrenecarboxaldehyde 1-Pyrenecarboxylic Acid 1-Pyrenemethanol 1,3,6,8-Tetrabromopyrene

Unit Size

B1919

1g

5g 1g 1g 5g 1g

1g 1g 200mg 5g 1g

B4563

5g 1g 1g 1g

25g 1g 5g 5g 25g 5g 1g 100mg 100mg 100mg 5g 5g 1g 1g 25g 1g 25g 5g 5g 5g 5g

Materials Chemistry

Product Name

A0632 A2180 B3956 B3957 B1495 B2807 C1637 D2167 D2160 D2168 D4187 D3167 D3169 E0939 N0419 N0838 P1625 P1448 P1687 P1221 T2716

Synthetic Organic Chemistry

Product No.

B1524

CH2Br

CH2Br

CH2Br

Naphthalenes CH2Br

B0618

B0619

B4463

B0621

B4580

B(OH)2

Br

OH

Br

Br

OH

Br Br

B3978

B4568

B4159

Br

D0101

Br

D4668 NH2

Br

Br OH HO

NH2

D4669

D2359

D4660

D4597

OH

Br

Br

Br

Br

E0933

Br

Br

Br

I0266

C CH

Br

Br

Br

D3624

D4154

Br

Br HO

Br

N0002 I

N0003 O C H

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

O C H

247

Building Blocks for Small Molecule Semiconductor

N0649 B(OH)2

N0946

N0052

N1009

P2290

B(OH)2

B(OH)2

NH2

B(OH)2

N0212

N0798

V0040 B(OH)2

B(OH)2

Materials Chemistry

Synthetic Organic Chemistry

N0630

NO2

CH CH2

Product No.

Product Name

B1919 B4563 B1524 B0618 B0619 B4463 B0621 B4580 B3978 B4568 B4159 D0101 D4668 D4669 D2359 D4660 D4597 D4154 D3624 E0933 I0266 N0002 N0003 N0630 N0649 N0052 N1009 N0798 N0946 N0212 P2290 V0040

1,4-Bis(bromomethyl)naphthalene (contains ca. 23% isomer) 1-(Bromomethyl)naphthalene 2-(Bromomethyl)naphthalene 1-Bromonaphthalene 2-Bromonaphthalene 4-Bromo-1-naphthaleneboronic Acid (contains varying amounts of Anhydride) 6-Bromo-2-naphthol 7-Bromo-2-naphthol 1-(4-Bromophenyl)naphthalene 2-(3-Bromophenyl)naphthalene 2-(4-Bromophenyl)naphthalene 1,5-Diaminonaphthalene 1,5-Dibromo-2,6-dihydroxynaphthalene 3,6-Dibromo-2,7-dihydroxynaphthalene 1,4-Dibromonaphthalene 1,5-Dibromonaphthalene 2,3-Dibromonaphthalene 2,6-Dibromonaphthalene 2,7-Dibromonaphthalene 2-Ethynylnaphthalene 1-Iodonaphthalene 1-Naphthaldehyde 2-Naphthaldehyde 1-Naphthaleneboronic Acid (contains varying amounts of Anhydride) 2-Naphthaleneboronic Acid (contains varying amounts of Anhydride) 1-Naphthylamine 3-(2-Naphthyl)phenylboronic Acid (contains varying amounts of Anhydride) 4-(1-Naphthyl)phenylboronic Acid (contains varying amounts of Anhydride) 4-(2-Naphthyl)phenylboronic Acid (contains varying amounts of Anhydride) 1-Nitronaphthalene 4-Phenylnaphthalene-1-boronic Acid (contains varying amounts of Anhydride) 1-Vinylnaphthalene (stabilized with TBC)

Unit Size

A2741

248

25g 1g 1g 1g 25g

CH3

N H

100g 5g 1g 5g 200mg 5g

25mL 5g 1g 5g 1g 5g 25g 1g 1g 200mg 25g 1g

B2429

Secondary Arylamines CH3

25g

1g 5g 5g 100g 5g

5g 25g 25g 500g 25g 1g 100g 5g 5g 5g 1g 500g 25g 5g 25g 1g 1g 1g 25g 100mg 25g 500mL 25g 25g 25g 100g 5g 5g 1g 500g 5g 5g

B2684

NH

Br

NH

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Br

Building Blocks for Small Molecule Semiconductor

B2803

B4664

B3949

D0632

Synthetic Organic Chemistry

CH3

B2685

CH3

CH3 C

NH

CH3

C CH3 CH3

D3398

CH3

N H

CH3

I CH3

D3845

NH

D0812

NH

NH

D0609

NH

NH

F0630

NH

NH

D1512

NH

D0950

CH3 NH

D3567

OCH3

NH

CH3

D0878

NH

CH3O

CH3

NH

M2069

NH

NH

CH3

NH

M1135

F

CH3

M1286

OCH3 NH

Materials Chemistry

D0872

Br

D2988

CH3 CH3

NH

I

D2986

CH3 NH

NH

CH3

CH3 NH

NH

OCH3

NH

OCH3

CH3

CH3

M2070

M1258

M1173

P1494

P1495

CH3 CH3

NH

OCH3

P1496

NH NH

NH

P1497

P1498

NH

P0197

P0198

NH

T2201

T2065 CH3

T1326

NH

T1831

T2891 NH

CF3

CH3

CH3O

N

NH HN

Product No.

Product Name

A2741 B2429 B2684 B2803 B4664 B2685

2-Anilino-9,9-dimethylfluorene Bis(4-biphenylyl)amine Bis(4-bromophenyl)amine Bis(4-tert-butylphenyl)amine Bis(9,9-dimethyl-9H-fluoren-2-yl)amine Bis(4-iodophenyl)amine

NH

NH

NH

NH

NH

CH3

NH

NH

Unit Size 1g 1g 1g 25g 1g 1g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

5g 5g 5g 500g 5g 5g

249

Materials Chemistry

Synthetic Organic Chemistry

Building Blocks for Small Molecule Semiconductor

Product No.

Product Name

B3949 D0632 D3398 D3845 D2986 D2988 D0812 D0872 D0878 D0609 D1512 D0950 D3567 F0630 M1135 M2069 M1286 M2070 M1258 M1173 P1494 P1495 P1496 P1497 P1498 P0197 P0198 T2201 T2065 T1326 T1831 T2891

4-Bromodiphenylamine 4,4'-Dimethoxydiphenylamine 2,4-Dimethyldiphenylamine 3,4-Dimethyldiphenylamine 1,1'-Dinaphthylamine 1,2'-Dinaphthylamine (purified by sublimation) N,N '-Di-2-naphthyl-1,4-phenylenediamine Diphenylamine N,N '-Diphenylbenzidine N,N '-Diphenyl-1,4-phenylenediamine m,m '-Ditolylamine p,p '-Ditolylamine N,N '-Di-p-tolylbenzidine 4-Fluorodiphenylamine 3-Methoxydiphenylamine 4-Methoxydiphenylamine 4-Methoxy-2-methyldiphenylamine 4-Methoxy-4'-methyldiphenylamine 3-Methyldiphenylamine 4-Methyldiphenylamine N-Phenyl-1-anthramine N-Phenyl-2-anthramine N-Phenyl-9-anthramine N-Phenyl-3-biphenylamine N-Phenyl-4-biphenylamine N-Phenyl-1-naphthylamine N-Phenyl-2-naphthylamine N-(p-Tolyl)-1-naphthylamine N-(p-Tolyl)-2-naphthylamine 3-Trifluoromethyl-4'-methoxydiphenylamine N,N ',N ''-Triphenyl-1,3,5-benzenetriamine N,N,N '-Triphenylbenzidine

Unit Size 5g 1g

1g 25g 25g 5g 25g 5g 5g 1g 1g 25g 5g 25g 5g 1g

1g

25g 25g

1g 5g 1g

A2858

A2624

B4550 NH2

Tertiary Arylamines

CH3

CH3

25g 5g 25g 25g 1g 5g 500g 500g 25g 500g 25g 25g 5g 5g 500g 25g 500g 25g 25g 5g 500mg 1g 5g 500mg 500mg 500g 500g 500mg 500mg 5g 25g 5g

Br

N

N

N Br

B3991

B1336

B4793

Cl

O C H

B2843

N

N

Br

N

N

N

N Br

O Br

B3089

C H O

Cl

B2844

B4299

C H

CH3O

OCH3

B4036

Br

Br

Br

N

N

N

N

N

Br

CH3

B2633

D3302

D3303

Br

Br

N

N Br

250

N

O

H C

B4008

Br

CH3

B4667

O H C

Br

D1910

D4755

Br

N

Br N CH3

N

CH3

Br

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Building Blocks for Small Molecule Semiconductor

D2172

D3537

D2737

E0894

I0490 C CH

C H

C H

I

N

N

T2891

CH3

CH3

T2332

I

N

N

N CH3

I0776

Synthetic Organic Chemistry

O

B(OH)2

O

T1361

T2310 Br

NH2

O C H

N

NH

N

N

N O

OCH3

CH3O

NH2

Br

Br

N

O

H C

C H

T2333 I

NO2

N

N

I

I

O2N

Materials Chemistry

T1724

H2N

NO2

Product No.

Product Name

A2858 A2624 B4550 B3991 B1336 B4793 B2843 B4667 B3089 B2844 B4299 B4008 B4036 B2633 D3302 D3303 D1910 D4755 D2172 D3537 D2737 E0894 I0490 I0776 T2891 T2332 T1361 T2310 T1724 T2333

2-Amino-N-[(1,1'-biphenyl)-4-yl]-N-(4-bromophenyl)-9,9-dimethylfluorene 4-Aminotriphenylamine N,N-Bis(4-biphenylyl)-N-(4-bromophenyl)amine 4-[N,N-Bis(4-bromophenyl)amino]benzaldehyde N,N '-Bis(4-chlorophenyl)-N,N '-diphenyl-1,4-phenylenediamine N,N '-Bis(4-formylphenyl)-N,N '-diphenylbenzidine Bis(4-formylphenyl)phenylamine (purified by sublimation) 4-Bromo-4',4''-dimethoxytriphenylamine 4-Bromo-4',4''-dimethyltriphenylamine 4-Bromo-4'-(diphenylamino)biphenyl N-(4-Bromophenyl)-N-phenyl-1-naphthylamine 2-Bromotriphenylamine 3-Bromotriphenylamine 4-Bromotriphenylamine 4,4'-Dibromo-4''-cyclohexyltriphenylamine 4,4'-Dibromo-4''-phenyltriphenylamine 4,4'-Dibromotriphenylamine 3,3'-Dimethyltriphenylamine 4-(N,N-Diphenylamino)benzaldehyde 4-(Diphenylamino)phenylboronic Acid (contains varying amounts of Anhydride) 4-(Di-p-tolylamino)benzaldehyde 4-Ethynyltriphenylamine N-(4'-Iodobiphenyl-4-yl)-N-(m-tolyl)aniline 4-Iodo-4',4''-dimethoxytriphenylamine N,N,N '-Triphenylbenzidine Tris(4-aminophenyl)amine Tris(4-bromophenyl)amine Tris(4-formylphenyl)amine Tris(4-iodophenyl)amine Tris(4-nitrophenyl)amine

Unit Size

A2789

1g

5g 200mg 25g 200mg 1g 1g 1g 5g 5g 1g 1g 5g 5g 25g 1g 1g 5g 5g 25g 5g 5g 1g 1g 5g 5g 5g 25g 500mg 25g 25g

5g

200mg 1g 1g 250mg 200mg 1g 5g

1g 1g 5g 1g 1g

1g 1g 1g

5g 1g

B4459

B4662

NH2

Br

Others

N

O

N

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

Br

251

Building Blocks for Small Molecule Semiconductor

Synthetic Organic Chemistry

B4599

B4686

B4671

B2387

B0838 Br

Br

Br

Br O

Br

H C

B4794

B4479

B4308

B4442

C3008 Br

Br

N

N N

N

Br

Materials Chemistry

Br

Cl

C2669

D4567

D4759

D3166

D4236 Br

O

O

O C H

Br

Br

O B(OH)2

O Br

D4801

D4835

D3743

H0923

Br I

O

I

H0907

Br

AcO

Br

OAc

P2110

O

Br

OAc

P1685

OH HO

Br Br

O

N H

N0603 OH

Br OAc

AcO

O

Br

H1201 OAc

H N

P2158

O

O

N

C H

. xH2O

N

HO

B(OH)2 OH

O

O

OH

P2290

T2792 B(OH)2

T3089

T3261

T2728 NH2

B(OH)2

CH3 O

CH3

O

CH3

B

B

O

O CH3

CH3

CH3 CH3 CH3

H2N

T3073

T2644

T3178

T2647

Br

Br

Br

Br

N

NH2

T3213 Br

COOH

Br

Br

N

Br

N Br

Br

Br

Br

Br

HOOC

COOH

Br

Br

T3084 I

I

252

I

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Building Blocks for Small Molecule Semiconductor

3-Aminofluoranthene 2-Bromodibenzofuran 2-Bromo-4,6-diphenylpyrimidine 3-Bromofluoranthene 6-Bromo-2-naphthaldehyde 2-Bromophenanthrene 3-Bromophenanthrene 9-Bromophenanthrene 2-(3-Bromophenyl)-1-phenylbenzimidazole 2-(4-Bromophenyl)-1-phenylbenzimidazole 5'-Bromo-m-terphenyl 2-Bromotriphenylene 4-Chloro-5'-phenyl-1,1':3',1''-terphenyl Cyclopenta[fg]tetracene-1,2-dione Dibenzofuran-4-boronic Acid (contains varying amounts of Anhydride) Dibenzofuran-2-carboxaldehyde 3,3'-Dibromobiphenyl 6,12-Dibromochrysene 2,7-Dibromotriphenylene 2,8-Diiododibenzofuran 3,6-Diphenyl-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione 2,3,6,7,10,11-Hexaacetoxytriphenylene 2,3,6,7,10,11-Hexabromotriphenylene 2,3,6,7,10,11-Hexahydroxytriphenylene Hydrate 5,12-Naphthacenequinone 6,13-Pentacenedione 3-Perylenecarboxaldehyde 4-(1-Phenyl-1H-benzimidazol-2-yl)phenylboronic Acid (contains varying amounts of Anhydride) 4-Phenylnaphthalene-1-boronic Acid (contains varying amounts of Anhydride) 5'-m-Terphenylboronic Acid (contains varying amounts of Anhydride) 4,4,5,5-Tetramethyl-2-(3-perylenyl)-1,3,2-dioxaborolane 4,4,5,5-Tetramethyl-2-[3-(triphenylen-2-yl)phenyl]-1,3,2-dioxaborolane 1,3,5-Tris(4-aminophenyl)benzene 1,3,5-Tris(3-bromophenyl)benzene 1,3,5-Tris(4-bromophenyl)benzene 2,4,6-Tris(4-bromophenyl)-1,3,5-triazine 1,3,5-Tris(4-carboxyphenyl)benzene 1,3,5-Tris(3,5-dibromophenyl)benzene 1,3,5-Tris(4-iodophenyl)benzene

Unit Size 1g 1g 200mg 1g 200mg 25g 1g 1g 5g 1g 200mg 200mg 1g 1g 5g 200mg 200mg 200mg 5g 100mg 1g 10g 5g 1g 1g 1g 200mg 200mg 1g 1g 1g 200mg 1g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

5g 5g 1g 5g 1g 1g 100mg 250g 5g 5g 25g 5g 1g 1g 5g 5g 25g 1g 1g 1g 25g 100mg 1g 5g 25g 25g 5g 5g 5g 1g 1g 1g 5g 5g 5g 200mg 5g 1g 5g

Materials Chemistry

Product Name

A2789 B4459 B4662 B4599 B4686 B4671 B2387 B0838 B4794 B4479 B4308 B4442 C3008 C2669 D4567 D4759 D3166 D4236 D4801 D4835 D3743 H0923 H1201 H0907 N0603 P1685 P2110 P2158 P2290 T2792 T3089 T3261 T2728 T3073 T2644 T3178 T2647 T3213 T3084

Synthetic Organic Chemistry

Product No.

253

Materials Chemistry

Synthetic Organic Chemistry

Ligands for Functional Metal Complex

Ligands for Functional Metal Complex Optically and electronically functional metal complexes exhibiting light absorption, emission, and magnetism have been well known. Such functional metal complexes show absorption (emission) by a charge transfer, electrical conduction, and magnetic properties based on d- or f-electrons of the metal center. Coordination modes of metal complexes are diverse from two-coordinate to eight-coordinate, and thus many coordination geometries are known. Here we list ligands to synthesize the functional metal complexes that are useful for electronics and dye-sensitizers. In particular, these ligands undergo more than bidentate chelation with a metal center forming a rigid structure. Many transition metals can be redox centers in the metal complex, because they can have several oxidation states. On the other hand, there are‘redox active ligands’that can function as redox centers. One can observe a variety of oxidation states in the transition metal complexes bearing a redox active ligand, because the redox center involves both of the metal and the coordinating ligand. In addition, a redox active ligand may interexchange electrons with a metal center. A typical example is valence tautomerism.1,2) The water oxidation catalyst developed by Tanaka . also requires a redox active ligand.3,4) Physical properties of a metal complex involving a redox active ligand are sometimes due to the π-electrons of the ligand. The metal complexes with a redox active dithiolene ligand have been studied on conductivity and magnetism based on the π-conjugated structure.5)

O M(II) O

O

-e-

M (I)

+e-

O

B0088

-e-

O

+e-

O

M (0)

B3509

B4509 O

HO C

C OH

N

B0470 CH3

B4092

. xH2O

B3314

N

D3413 F

N N

N

D1922

C ONa

N

N

CH3

N

O

NaO C

N

Phenylpyridines

B0841

O

O

CH3

N

N

N

(CH2)3CH3

C CH3

F

CH3

H1265

M2101

M2001

M0932 CH3

N

N

(CH2)5CH3

N

N

CH3

N

OCH3

P1731

P1039

P2057

P1301

N N

254

P1889 O

O

C OH

C H

N N

N

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Ligands for Functional Metal Complex

P1671

T1228

Synthetic Organic Chemistry

O C H

N

N

CH3

Product Name

B0088 B3509 B4509 B0841 B0470 B4092 B3314 D3413 D1922 H1265 M2101 M2001 M0932 P1731 P1039 P2057 P1301 P1889 P1671 T1228

Benzo[h]quinoline 2,2'-Bicinchoninic Acid Bicinchoninic Acid Disodium Salt Hydrate 2,2'-Bi-4-lepidine 2,2'-Biquinoline 2-(4-tert-Butylphenyl)pyridine 2-Butyl-6-phenylpyridine 2-(2,4-Difluorophenyl)pyridine 2,6-Diphenylpyridine 2-Hexyl-6-phenylpyridine 2-(4-Methoxyphenyl)pyridine 2-Methyl-6-phenylpyridine 3-Methyl-2-phenylpyridine 1-Phenylisoquinoline 2-Phenylpyridine 2-Phenylquinoline 2-Phenylquinoline-4-carboxylic Acid 3-(2-Pyridyl)benzaldehyde 4-(2-Pyridyl)benzaldehyde 2-(p-Tolyl)pyridine

Unit Size 5g 1g 1g 1g 200mg 1g 5g 1g

1g 5g

A1005

B3324

C0645

. 2HCl

Quinolinols

N

N

D0412

D3819

N

Cl

N

M0420

OH

OH

OH

H1272

F0038 I

N

OH

OH

D1736

Cl

Br

N

OH

OH

Br

Cl

Br

NH2

D0208

5g 1g 5g 1g 5g 1g

25g 5g 5g 100mg 5g 1g 1g 5g 25g 1g 25g 5g 25g 5g 25g 5g 25g 1g 5g 25g

Materials Chemistry

Product No.

I

F

N

N

OH

N0270

OH

H0305

Q0017

NO

N OH

O

N OH

CH3

N OH

Product No.

Product Name

A1005 B3324 C0645 D0208 D0412 D3819

5-Amino-8-hydroxyquinoline Dihydrochloride 5-Bromo-8-hydroxyquinoline 5-Chloro-8-hydroxyquinoline 5,7-Dibromo-8-hydroxyquinoline 5,7-Dichloro-8-hydroxyquinoline 2,8-Dihydroxyquinoline

N OH

. H2SO4 . H2O

N OH

2

Unit Size 5g 5g 25g 5g 5g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

25g 25g 250g 25g 25g 25g

255

Materials Chemistry

Synthetic Organic Chemistry

Ligands for Functional Metal Complex

Product No.

Product Name

D1736 F0038 H1272 M0420 N0270 H0305 Q0017

5,7-Diiodo-8-hydroxyquinoline 5-Fluoro-8-quinolinol 8-Hydroxyquinoline N-Oxide 2-Methyl-8-quinolinol 5-Nitroso-8-hydroxyquinoline 8-Quinolinol 8-Quinolinol Sulfate Monohydrate

Unit Size

25g

25g 25g

A0267

A1593

A0364

SH

OH

. HCl

NH2

A0335 OH

NH2

OH

NH2

Redox Active Ligands

A0365

25g 5g 25g 500g 25g 500g 500g

1g 5g 100g

B1322

B1199 SH

OH NH2

SH

NH2

. HCl

B2228 O

S

S

C

NC(CH2)2S

S

S

S

C

NC(CH2)2S

S

S

S O

P0317

T0970

D2022 O

OH

Cl

OH

O

Cl

Cl

NC

CN

NH2

. 2HCl

H2N

H2N

NH2

NH2

SH

D2430

D3252

OH

D1045

NH2

Cl

D1888

D1335 SH

D2299

D0593

O

H2N

. 2HCl OH

O H 3C H 3C C

NH2

C CH3

H3C

D1930

NC

OH

S

CH3 S

NC

OH

CH3

H0907

H1177

M0413

OH OH

NaS NC

SNa

HO

CN

HO

P0168 O

T2806

O

256

N

T0266

NH2 NH2

O

O

CH3

OH

O

O

OH

SH

. xH2O

P1973

N0041 OH

OH

OH

P0080

OH

OH

O

NC NC

S

S

S

S

S

S

S

S

HS CN CN

HS

CH3

N

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Ligands for Functional Metal Complex

2-Aminobenzenethiol 3-Amino-2-naphthol 1-Amino-2-naphthol Hydrochloride 2-Amino-1-naphthol Hydrochloride 2-Aminophenol 1,2-Benzenedithiol 4,5-Bis(benzoylthio)-1,3-dithiole-2-thione 4,5-Bis(2-cyanoethylthio)-1,3-dithiole-2-thione Catechol o-Chloranil 2,5-Diamino-1,4-benzenedithiol Dihydrochloride Diaminomaleonitrile 2,3-Diaminonaphthalene 4,6-Diaminoresorcinol Dihydrochloride 3,5-Di-tert-butyl-1,2-benzoquinone 4,5-Dicyano-1,3-dithiol-2-one 1,2-Dihydroxynaphthalene 2,3-Dihydroxynaphthalene Disodium Dimercaptomaleonitrile 2,3,6,7,10,11-Hexahydroxytriphenylene Hydrate 2-Hydroxybenzenethiol 4-Methylcatechol 1,2-Naphthoquinone 9,10-Phenanthrenequinone 1,10-Phenanthroline-5,6-dione 1,2-Phenylenediamine 2,3,6,7-Tetrakis(2-cyanoethylthio)tetrathiafulvalene Toluene-3,4-dithiol

Unit Size 25mL 100mL 500mL 5g 25g 1g 5g 25g 100g 500g 1g 5g 1g 5g 1g 25g 100g 5g 25g 5g 25g 25g 100g 500g 1g 5g 5g 25g 5g 25g 1g 1g 5g 25g 250g 1g 5g 1g 5g 5g 25g 25g 500g 5g 25g 5g 25g 1g 5g 25g 100g 500g 100mg 1g 1g 5g 25g

A2759

B2812

Materials Chemistry

Product Name

A0267 A1593 A0364 A0365 A0335 B1322 B1199 B2228 P0317 T0970 D2022 D1335 D1045 D1888 D2430 D3252 D2299 D0593 D1930 H0907 H1177 M0413 N0041 P0080 P1973 P0168 T2806 T0266

Synthetic Organic Chemistry

Product No.

B4101 N

H2N

N

N

Other Ligands

N

N H

N H NH2

Br Br

B2577

C2027

C2811

C2045

F0851 N

Br

N

N N H

N

N

Cl

N

N N H

N H

Cl

N

N

N N

Cl

Cl CN

F0427

H0738

H0973

H0291

HO

N

N

N H

I0818 N

OH

OH

O

N N

O

S

C H

F

I0735

M0669 I

N

N N H

N0859

CH3

P1105

P1130

N H

N

N

N

N

N H

N H

S

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

257

Ligands for Functional Metal Complex

Synthetic Organic Chemistry

P2030

P0684

P0188

P1945

P1109

N N

N

N N H

P1816

N H

T2486

N

N

Materials Chemistry

CH3

N N

2Br

CH3

N H

N

N CF3

CH3

Product Name

A2759 B2812 B4101 B2577 C2027 C2811 C2045 F0851 F0427 H0738 H0973 H0291 I0818 I0735 M0669 N0859 P1105 P1130 P2030 P0684 P0188 P1945 P1109 P1816 T2486 T2982

5-Amino-2-(4-aminophenyl)benzimidazole 2-(4-Bromophenyl)benzimidazole 1-(4-Bromophenyl)imidazole 5-(2-Bromophenyl)-1H-tetrazole 2-(4-Chlorophenyl)benzimidazole 5-(2-Chlorophenyl)-1H-tetrazole 1-(4-Cyanophenyl)imidazole Fenclorim 2-(4-Fluorophenyl)indole 10-Hydroxybenzo[h]quinoline 2-(2-Hydroxyphenyl)benzothiazole 2-(2-Hydroxyphenyl)benzoxazole 4-(1-Imidazolyl)benzaldehyde 5-(2-Iodophenyl)-1H-tetrazole 4-Methyl-2-phenylimidazole 2-(2-Naphthyl)indole 2-Phenylbenzimidazole 2-Phenylbenzothiazole 1-Phenylimidazole 2-Phenylimidazole 2-Phenylindole 2-Phenylpyrimidine 5-Phenyltetrazole 1,1'-(2,6-Pyridinediyl)bis(3-methylimidazolium) Dibromide 5-(p-Tolyl)-1H-tetrazole 1-[2-(Trifluoromethyl)phenyl]imidazole

Unit Size 1g 1g 1g 5g 1g 1g 1g 1g 5g 1g 1g 25g 1g

1g 25g 200mg 25g 100g 1g 5g

Bipyridine & Terpyridine (see also p.98) Phenanthroline (see also p.100) References

258

N

N

N

Product No.

1) 2) 3) 4) 5)

N H

N

T2982 N

N

N

N

Review: T. Tezgerevska, K. G. Alley, C. Boskovic, C. G. Pierpont, O.-S. Jung, . 1995, , 4281. T. Wada, K. Tsuge, K. Tanaka, . 2000, T. Wada, K. Tsuge, K. Tanaka, . 2001, , 329. Review: R. Kato, . 2004, , 5319.

. 2014,

, 23.

, 1479.

Availability or specification of the listed products are subject to change without prior notice.

5g 5g 5g 25g 5g 5g 5g 5g 25g 5g 25g 25g 5g 5g 500g 5g 25g 5g 5g 100g 250g 1g 500g 5g 25g 1g

Photochromic Compounds

NO2 hν N

O

NO2

hν or Δ

N

O

Spiropyran [T0366] F

F

F

F

F

F F

F

F

F

F

hν (UV)

F

hν (Vis) S

S

S

S

Diarylethene [B2629]

Hayashi and Maeda observed photochromism of an imidazole dimer, hexaarylbiimidazole (HABI).5) A light irradiation to HABI undertakes dissociation of the dimer. The photochromic mechanism is different from those of the others doing photo isomerizations. A triphenylimidazolyl radical formed by the dissociation thermally recombines to reform the original HABI, thus this is a T-type photochromism. The triphenylimidazolyl radical is also useful as a photopolymerization initiator.6) H1042

T0344 CH3

CH3 CH3

Spiropyrans

N

T0370

N

NO2

O

HOH2CH2C

T0416

T0423 CH3

N

CH3

O CH3 CH3O

N

CH3

N

O

O

Br

CH3

T0366

CH3

CH3 CH3

O

N

CH3

CH3

CH3

T1259

CH3

CH3

N O

CH3

CH3 CH3

N

O

NO2

CH3

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

259

Materials Chemistry

Chromism is a phenomenon that reversibly changes optical properties (eg. photo absorption and emission) by an external stimulus. A molecular structure changes in many cases while chromism occurs, and then refractive index, dielectricity, redox potentials, and melting point also change. Photochromism is a photo-induced chromism. Photochromic materials are further developed for a light-modulating materials, optical recording media, optical switches, and functional inks. A structural isomerization during photochromism involves photo-induced geometrical isomerizations (eg. isomerization) and photo-induced ring-opening and -closure reactions. Fischer . first reported the photochromic behavior of spiropyrans.1) UV irradiation to a spiropyran undertakes a ring-opening of the spiro carbon. The structural change leads to a blue shift of photo absorption up to the visible region. Irie . first observed photochromism of diarylethenes.2) The diarylethene also shows photo-induced ring-opening and -closure reactions. UV irradiation to the diarylethene undertakes a ring-closure (with coloration) whereas a spiropyran does a ring-opening (with coloration) by UV irradiation. The ring-opened spiropyran thermally closes the ring (T-type). On the other hand, the ring-closed diarylethene is thermally stable but opens to form the original compound by visible light irradiation (P-type). It is well known that diarylethene is a photochromic compound with high photo sensitivity and repetition durability.3) A fulgide is also a P-type photochromic compound exhibiting a ring-closure by a photo irradiation.4)

Synthetic Organic Chemistry

Photochromic Compounds

Synthetic Organic Chemistry

Photochromic Compounds

Product No.

Product Name

H1042 T0344 T0370 T0416 T0423 T1259 T0366

1-(2-Hydroxyethyl)-3,3-dimethylindolino-6'-nitrobenzopyrylospiran 1,3,3-Trimethylindolinobenzopyrylospiran 1,3,3-Trimethylindolino-6'-bromobenzopyrylospiran 1,3,3-Trimethylindolino-8'-methoxybenzopyrylospiran 1,3,3-Trimethylindolino-β-naphthopyrylospiran 1,3,3-Trimethylindolinonaphthospirooxazine 1,3,3-Trimethylindolino-6'-nitrobenzopyrylospiran

Unit Size

Materials Chemistry

D3618

1g 1g

5g 5g 1g 25g 5g 1g 25g

1g 1g 1g

D3619 NH2

O NH2

Spiroperimidines

HN

NH

HN

Product No.

Product Name

D3618 D3619

2,3-Dihydro-2-spiro-4'-[8'-aminonaphthalen-1'(4'H)-one]perimidine (contains o-form) 2,3-Dihydro-2-spiro-7'-[8'-imino-7',8'-dihydronaphthalen-1'-amine]perimidine

Unit Size

B2629

B2287 F

CH3

Diarylethenes

S

F

F

F

CH3 CH3

F CH3

B1535

F

F

F

F

F

O

S

CH3 CH3

O

O CH3

CH3 S

CH3

S

CH3 CH3

S

CH3

B1536 O

H N

NC

O CH3

CH3 CH3

100mg 100mg

B1534

F

F

S

260

NH NH

S

CH3 CH3

S

CH3

CN CH3

CH3 CH3

S

CH3 CH3

S

CH3

Product No.

Product Name

B2629 B2287 B1534 B1535 B1536

1,2-Bis(2,4-dimethyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluoro-1-cyclopentene 1,2-Bis[2-methylbenzo[b]thiophen-3-yl]-3,3,4,4,5,5-hexafluoro-1-cyclopentene 2,3-Bis(2,4,5-trimethyl-3-thienyl)maleic Anhydride 2,3-Bis(2,4,5-trimethyl-3-thienyl)maleimide cis-1,2-Dicyano-1,2-bis(2,4,5-trimethyl-3-thienyl)ethene

Unit Size

Availability or specification of the listed products are subject to change without prior notice.

100mg 100mg 100mg 100mg 1g

1g 1g 1g 1g 5g

Photochromic Compounds

A2869

Synthetic Organic Chemistry

O CH3

Fulgide

O

CH3 O CH3

Product No.

Product Name

A2869

Aberchrome 670

O

Unit Size 200mg

1g

Materials Chemistry

B1225 Cl

Hexaarylbiimidazole

N

N N

N Cl

Product No.

Product Name

B1225

2,2'-Bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole

Unit Size 25g

References 1) 2) 3) 4) 5) 6)

E. Fischer, Y. Hirshberg, . 1952, 4522. Review: M. Irie, . 2000, , 1685. K. Matsuda, M. Irie, TCIMAIL 2003, number , 2. J. Harada, R. Nakajima, K. Ogawa, . 2008, , 7085. K. Maeda, T. Hayashi, . 1969, , 3509. Review: B. M. Monroe, G. C. Weed, . 1993, , 435.

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

261

Materials Chemistry

Synthetic Organic Chemistry

Liquid Crystal Materials

Liquid Crystal Materials Liquid crystals have properties between those of conventional liquid and those of solid crystal. For instance, a liquid crystal shows fluidity like a liquid, but it also demonstrates optical anisotropy like a crystal. Liquid crystal molecules are directionally oriented, but positionally not oriented. Small moleculebased and polymer-based liquid crystals are known. The structure of a liquid crystal involves rigid π-electron systems bearing flexible long alkyl chains. Many liquid crystal molecules are calamitic shaped with a group for polarization, but planar molecules are also known. We can control the temperature which shows a liquid crystal phase by modifying the length of alkyl chain. A practical liquid crystal has a mesophase around room temperature. In addition to an application for a liquid crystal display, liquid crystal materials are expected to be organic semiconductors. A semiconductor having a liquid crystal phase, the so-called liquid crystal semiconductor, spontaneously undergoes a molecular orientation and self-assembly.1,2) The various liquid-crystal phases can be characterized by the type of ordering. Among them, there are mainly nematic, smectic, cholesteric, and discotic phases. We can introduce chirality into a liquid crystal molecule giving chiral nematic and chiral smectic phases.

Nematic Phase

Smectic Phase

Cholesteric Phase (Chiral Nematic Phase)

Discotic Phase (Columnar Phase)

(1) Nematic phase Calamitic shaped molecules are oriented one-dimensionally. The individual molecule can be relatively movable along the long axis direction. This phase belongs to the most flexible liquid crystal with large fluidity and small viscosity. Calamitic shaped cyanobiphenyls with large dielectric anisotropy (Δε) enable control of the molecular orientation by applying an electrical field. A liquid crystal display of a twisted nematic (TN) system3) is fabricated from a nematic liquid crystal. (2) Smectic phase There is a two-dimensional layered structure caused by more positional limitations compared with that of a nematic phase. A smectic phase is harder than a nematic phase, because the movable range of the unit molecules is relatively narrow. A nematic phase sometimes changes to a smectic phase by decreasing the temperature. Diversity of the layered structures demonstrates many kinds of smectic phases. (3) Cholesteric phase (Chiral nematic phase) This phase is usually observed from cholesterol derivatives. The unit molecules are oriented onedimensionally similar to a normal nematic phase, but the molecular orientation shows a twisted helical arrangement between layers. This is due to an asymmetric carbon (chiral center) in the cholesterol molecule. Accordingly, a cholesteric phase is called a chiral nematic phase. This chiral phase exhibits optical rotation, selective optical scattering, circular polarization, and dichroism. Recently, a research development on a‘blue phase’received much attention.4) This phase is observed between temperatures of the cholesteric phase and an isotropic liquid. One difficulty is that we can find the blue phase in a narrow temperature range of 1-2 degrees. However, one can widen the temperature range more than several dozens of degrees, when a polymer slightly forms in the blue phase (polymer-stabilized blue phase).5)

262

Availability or specification of the listed products are subject to change without prior notice.

Liquid Crystal Materials

Cyanobiphenyls & Analogs

Nematic & Smectic Liquid Crystals

H0812

CH3(CH2)6

C1606

CN

C2910

CH3(CH2)4

C2618

CH3(CH2)6O

CN

C2911

A2568

CN

C1550

CH3(CH2)7O

CN

D4534

CN

CH3CH2CH2O

CN

CH3(CH2)4

CN

D4535

CH3(CH2)4O

CN

P2150

CH3(CH2)4

F F

CH3(CH2)4

CN

C1551

F CH3(CH2)4

CH3(CH2)4

Materials Chemistry

A1828

O

O

F

CH3CH2CH2

O

O

(CH2)4CH3

Product No.

Product Name

A1828 A2568 H0812 C1606 C2618 C1550 C1551 C2910 C2911 D4534 D4535 P2150

4-(trans-4-Amylcyclohexyl)benzonitrile 4'-(trans-4-Amylcyclohexyl)biphenyl-4-carbonitrile 4-Cyano-4'-heptylbiphenyl 4-Cyano-4'-heptyloxybiphenyl 4-Cyano-4'-n-octyloxybiphenyl 4-Cyano-4'-pentylbiphenyl 4-Cyano-4'-pentyloxybiphenyl 4-Cyano-4''-pentyl-p-terphenyl 4-Cyano-4'-propoxy-1,1'-biphenyl 3,4-Difluoro-4'-(trans-4-pentylcyclohexyl)biphenyl 3,4-Difluoro-4'-(trans-4-propylcyclohexyl)biphenyl (R)-1-Phenyl-1,2-ethanediyl Bis[4-(trans-4-pentylcyclohexyl)benzoate]

Unit Size

A0608

Carbonates

CH3CH2O

5g 1g 1g

1g

5g 5g 1g 1g 1g 5g 5g 200mg

25g 5g 5g 1g 25g 25g 5g 5g 5g 25g 25g 1g

E0257

O O C

O O C O(CH2)4CH3

O CH3CH2O

O C

O O C OCH2CH3

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

Synthetic Organic Chemistry

(4) Discotic phase Formation of a discotic phase requires a discotic aromatic molecule such as phthalocyanine,6) triphenylene,7) hexabenzocoronene8) and so on, although nematic and smectic phases require calamitic molecules. A discotic molecule usually forms a one-dimensional columnar structure (columnar phase) by stacking the molecules. A research area on organic electronics focuses on the discotic phase, because electrical conduction may occur along the molecular stacking direction. On the other hand, a rare example was reported that a chemical modification of a discotic molecule provided a three-dimensionally stacked cubic phase,9) whereas discotic molecules normally stack one-dimensionally.

263

Materials Chemistry

Synthetic Organic Chemistry

Liquid Crystal Materials

Product No.

Product Name

A0608 E0257

Amyl 4-(4-Ethoxyphenoxycarbonyl)phenyl Carbonate 4-(4-Ethoxyphenoxycarbonyl)phenyl Ethyl Carbonate

Unit Size

P0896

B1586

CH3(CH2)4

B0375

O C O

CH3(CH2)3

OCH2CH3

B1092

O(CH2)3CH3

O C O

CH3(CH2)4

Product Name

264

C O

C O

OCH3

(CH2)7CH3

1g

CH N

CN

NC

CH3(CH2)3O

CH N

O(CH2)3CH3

NC

1g 1g 5g 1g 1g 1g 5g 1g 5g 25g

B0252

CH N

O C CH3

C0744

O C O(CH2)3CH3

CH2 CHCH2CH2O

O

B0372

CH3(CH2)4O

CH

O(CH2)5CH3

1g

C0743

CH

O

C O

Unit Size

B0253

CH N

CN

M2106

CH3(CH2)4

O(CH2)7CH3

4-Butoxyphenyl 4-Pentylbenzoate 4-Cyanophenyl 4-(3-Butenyloxy)benzoate 4-Cyanophenyl 4-Heptylbenzoate 4-Ethoxyphenyl 4-Butylbenzoate 4-(Hexyloxy)phenyl 4-Butylbenzoate 4-Hexyloxyphenyl 4-Pentylbenzoate 4-Methoxyphenyl 4-(3-Butenyloxy)benzoate 4-n-Octyloxyphenyl 4-Butylbenzoate 4-n-Octyloxyphenyl 4-Pentylbenzoate 4-Octylphenyl Salicylate

CH3O

C O

OH

C O

P0896 B1586 H0810 B0375 B1091 P0897 M2106 B1092 P0898 S0016

B0255

CH3(CH2)6

S0016

Product No.

Schiff Bases

CN

O

O(CH2)5CH3

O

O(CH2)7CH3

C O

CH2 CHCH2CH2O

P0897

P0898

O C O

O

O

C O

B1091

CH3(CH2)3

H0810

O

Phenyl Esters

CH3(CH2)3

1g 1g

CH3(CH2)3O

CH

N

CN

C0742

CH N

OCH2CH3

NC

Availability or specification of the listed products are subject to change without prior notice.

CH N

O(CH2)5CH3

Liquid Crystal Materials

E0254

E0262

H0419

CH3CH2O

CH N

(CH2)3CH3

M0581

M0602

CH3CH2O

CH

N

CN

M0583

CH N

CN

CH N

O C CH3

M0582

CH3O

CH CHCOOCH2CH3

CH N

N N

M0275

CH3O

CH

N

CN

B0250

Materials Chemistry

M0603

CH3O

CH N

M0604

O CH3(CH2)5O

CH3O

Synthetic Organic Chemistry

O C CH3

CH N

CH3CH2O

E0240

OH CH3O

CH

N

CH3O

CH CH

CH N

CH3O

CH N

(CH2)3CH3

CH3O

CH N

(CH2)3CH3

B0871

CH3CH2O

N CH

CH N

OCH2CH3

Product No.

Product Name

B0253 B0372 B0252 B0255 C0743 C0744 C0742 E0254 E0262 E0240 M0602 H0419 M0581 M0583 M0604 M0603 M0582 M0275 B0250 B0871

4'-(Amyloxy)benzylidene-4-cyanoaniline N-(4-Butoxybenzylidene)-4-acetylaniline 4'-Butoxybenzylidene-4-cyanoaniline Butyl 4-[(4-Methoxybenzylidene)amino]cinnamate 4'-Cyanobenzylidene-4-butoxyaniline 4'-Cyanobenzylidene-4-ethoxyaniline 4'-Cyanobenzylidene-4-hexyloxyaniline N-(4-Ethoxybenzylidene)-4-acetylaniline 4'-Ethoxybenzylidene-4-butylaniline 4'-Ethoxybenzylidene-4-cyanoaniline Ethyl 4-[(4-Methoxybenzylidene)amino]cinnamate 4'-Hexyloxybenzylidene-4-cyanoaniline N-(4-Methoxybenzylidene)-4-acetoxyaniline 4-[(4-Methoxybenzylidene)amino]azobenzene 4-[(4-Methoxybenzylidene)amino]benzonitrile 4-[(Methoxybenzylidene)amino]stilbene N-(4-Methoxybenzylidene)aniline N-(4-Methoxybenzylidene)-4-butylaniline N-(4-Methoxy-2-hydroxybenzylidene)-4-butylaniline Terephthalbis(p-phenetidine)

Unit Size

A0554

Azoxybenzenes

CH3O

1g 1g 1g 1g 1g 1g Price on request 1g 25g 500g 1g 1g 1g 25g Price on request 1g 1g 5g 25g 25g 1g 5g 25g

A0683

N N O

OCH3

CH3CH2O

D1092

N N O

OCH2CH3

CH3(CH2)5O

N

N

O(CH2)5CH3

O

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

265

Liquid Crystal Materials

Synthetic Organic Chemistry

D1093

D1096

CH3(CH2)4O

N

N

O(CH2)4CH3

D0553

CH3(CH2)3O

N

O

O(CH2)3CH3

N

N

O(CH2)8CH3

N

O(CH2)11CH3

O CH3CH2O C

O C OCH2CH3

N N O

D1094

CH3(CH2)7O

N

O

N

O(CH2)7CH3

CH3CH2CH2O

O

Product No.

Product Name

A0554 A0683 D1092 D1093 D1096 D0553 A1065 D1518 D1123 D1094

4,4'-Azoxydianisole 4,4'-Azoxydiphenetole 4,4'-Bis(hexyloxy)azoxybenzene 4,4'-Diamyloxyazoxybenzene 4,4'-Dibutoxyazoxybenzene 4,4'-Didodecyloxyazoxybenzene Diethyl Azoxybenzene-4,4'-dicarboxylate 4,4'-Dinonyloxyazoxybenzene 4,4'-Di-n-octyloxyazoxybenzene 4,4'-Dipropoxyazoxybenzene

N N

OCH2CH2CH3

O

Unit Size 5g 1g

25g 5g 1g 1g 1g 5g 1g 100mg 1g 5g 5g

T0697

Others

N

O

D1123

CH3(CH2)8O

CH3(CH2)11O

O

D1518

Materials Chemistry

N

A1065

CH3O

T0699

CH N

C4H9

CH3O

CH N

C5H11

Product No.

Product Name

T0697 T0699

Liquid Crystal, TK-LQ 2040 Electric effect type, Mesomorphic range:20-40℃ [Nematic Liquid Crystal] Liquid Crystal, TK-LQ 3858 Electric effect type, Mesomorphic range:38-58℃ [Nematic Liquid Crystal]

Unit Size 1g 1g

C0319 CH3 H3C

Cholesteryl Compounds

Cholesteric Liquid Crystals

CH3 CH3

H3C

CH3COO

C0320

C0668 CH3 H3C

CH3

H3C H3C

CH3

H3C BzO

266

C0694 CH3

CH3

H3C

CH3

H3 C

CH3(CH2)2COO

C0617 CH3

H3C H3C

CH3

H3C

ClCOO

H3C PhCH=CHCOO

Availability or specification of the listed products are subject to change without prior notice.

CH3 CH3

Liquid Crystal Materials

C0618

C1260

CH3

H3C

CH3

H3C

CH3

H3C

CH3

H3C

Cl Cl

CH3(CH2)8COO

C0672

H3C

COO

C0619

CH3(CH2)5COO

C0692 H3C H3C

CH3

H3C H3 C

CH3

CH3 H3C

CH3

COOH

CH3

H3C

H3C H3C

CH3

H3C

CH3

CH3 CH3

CH3 H3C

H 3C

H3C

O

C0559

(CH2)7

O

(CH2)4CH3

C0322 H3C

CH3(CH2)6COO

(CH2)12CH3

N0347

C0693

CH3

H3C

CH3 H3C

CH3

H3C

CH3

CH3 H3C

CH3

H3C

O

CH3

CH3

CH3

H3C

CH3

CH3

H3C

H3 C

CH3(CH2)14COO

(CH2)7

CH3 CH3

H3 C

O

O

CH3(CH2)10COO

O

CH3 CH3

C0334

CH3

H3C

H3C

HOCO(CH2)2COO

C0675 CH3

H3C

Materials Chemistry

C0321 H3C H3C

CH3 CH3

H3 C

COO

Ph(CH2)2COO

C0620

C0674

CH3

H3C

H3C

CH3(CH2)4COO

CH3

H3C

HCOO

C0673

CH3

H3C H3C

CH3

Synthetic Organic Chemistry

CH3 H3C

CH3

H3C H3 C

C0671

CH3(CH2)7COO

PhCH2COO

(CH2)7CH3

C0676

C0323 CH3

C0677

CH3

H3C

CH3 H3C

CH3

H 3C

CH3

CH3 H3C

CH3

H3C CH3(CH2)16COO

CH3CH2COO

C0695 CH3 H3C

CH3 CH3

H 3C

H3C CH3(CH2)3COO

CH3 H

CH3

H H

H

Br

C0610 CH3 H3C H3C

CH3 H

CH3

H H

H

Cl

Product No.

Product Name

C0319 C0320 C0668 C0694 C0617 C0618 C1260 C0671 C0672 C0673 C0619 C0692 C0674 C0620

Cholesterol Acetate Cholesterol Benzoate Cholesterol Butyrate Cholesterol Chloroformate Cholesterol trans-Cinnamate Cholesterol Decanoate Cholesterol 2,4-Dichlorobenzoate Cholesterol Formate Cholesterol Heptanoate Cholesterol Hexanoate Cholesterol Hydrocinnamate Cholesterol Hydrogen Phthalate Cholesterol Hydrogen Succinate Cholesterol Laurate

Unit Size 25g 25g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

500g 25g 500g 25g 25g 25g 25g 10g 25g 25g 10g 10g 10g 25g

267

Materials Chemistry

Synthetic Organic Chemistry

Liquid Crystal Materials

Product No.

Product Name

C0321 C0675 C0334 C0559 C0322 N0347 C0693 C0676 C0323 C0677 C0695 C0610

Cholesterol Linoleate Cholesterol Myristate Cholesterol n-Octanoate Cholesterol Oleate Cholesterol Palmitate Cholesterol Pelargonate Cholesterol Phenylacetate Cholesterol Propionate Cholesterol Stearate Cholesterol Valerate Cholesteryl Bromide from Beef Fat Cholesteryl Chloride from Beef Fat

Unit Size

25g

25g 10g 25g

C0720

C0718 CH3 H3C

Cholesteryl Carbonates

CH3

CH3 H3C

H3C

O

CH3

CH3

H3C

C0717

CH3

H3C

CH3 H3C

CH3

H3C

O CH3(CH2)6O C O

CH3 H3C

CH3 CH3

O

(CH3)2CHCH2O C O

B0256

(CH3)2CHO C O

C0721

C0691 CH3

CH3 H3C

CH3 CH3

H3 C

CH3 H3C

CH3

H3C

CH3

O

O

O

O

CH3(CH2)7O C O

CH3(CH2)8O C O

O

Product No.

Product Name

C0720 C0718 C0716 B0264 C0725 C0719 C0717 C0715 B0256 C0721 C0691

Cholesterol Amyl Carbonate Cholesterol Butyl Carbonate Cholesterol Ethyl Carbonate Cholesterol Heptyl Carbonate Cholesterol Hexyl Carbonate Cholesterol Isobutyl Carbonate Cholesterol Isopropyl Carbonate Cholesterol Methyl Carbonate Cholesterol Nonyl Carbonate Cholesterol n-Octyl Carbonate Cholesterol Oleyl Carbonate

O(CH2)8

(CH2)7CH3

Unit Size 1g

1g 10g

H1449

H1450 O(CH2)7CH3

O(CH2)5CH3

O(CH2)7CH3

O(CH2)5CH3

Discotic Liquid Crystals

CH3(CH2)7O

CH3(CH2)5O CH3(CH2)5O

CH3(CH2)7O

O(CH2)5CH3 O(CH2)5CH3

268

CH3

CH3

H3C

H3C

CH3O C O

CH3

H3C

CH3

CH3 H3C

CH3 CH3

H3C

H3C O

O CH3(CH2)5O C O

C0715

CH3CH2O C O

C0719

CH3

CH3 CH3

H3C

O CH3(CH2)3O C O

C0725 CH3 H3C

CH3 H3C

CH3 CH3

H3C

O

25g 25g 25g 500g 25g 500g 10g 25g 500g 10g 10g 25g

C0716

CH3

CH3(CH2)4O C O

B0264

10g 5g 100g

O(CH2)7CH3 O(CH2)7CH3

Availability or specification of the listed products are subject to change without prior notice.

10g 10g 10g 10g 10g 10g 10g 10g 10g 10g 25g

Liquid Crystal Materials

Product Name

H1449 H1450

2,3,6,7,10,11-Hexakis(hexyloxy)triphenylene 2,3,6,7,10,11-Hexakis[(n-octyl)oxy]triphenylene

Unit Size 200mg 200mg

Synthetic Organic Chemistry

Product No.

1g 1g

References 1) 2) 3) 4) 5) 6) 7) 8) 9)

M. Funahashi, J. Hanna, . 1997, , 429. T. Yasuda, T. Shimizu, F. Liu, G. Ungar, T. Kato, . 2011, , 13437. M. Schadt, W. Helfrich, . 1971, , 127. 1973, D. Coates, G. W. Gray, , 115. H. Kikuchi, M. Yokota, Y. Hisakado, H. Yang, T. Kajiyama, . 2002, , 64. 2011, E. Venuti, R. G. D. Valle, I. Bilotti, A. Brillante, M. Cavallini, A. Calo`, Y. H. Geerts, , 12150. S. K. Pal, S. Setia, B. S. Avinash, S. Kumar, . 2013, , 1769. L. Piot, C. Marie, X. Feng, K. Müllen, D. Fichou, . 2008, , 3854. M. A. Alam, J. Motoyanagi, Y. Yamamoto, T. Fukushima, J. Kim, K. Kato, M. Takata, A. Saeki, S. Seki, S. Tagawa, T. Aida, . 2009, , 17722.

Materials Chemistry

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

269

Materials Chemistry

Synthetic Organic Chemistry

Building Blocks for Liquid Crystals

Building Blocks for Liquid Crystals The first nematic liquid crystal materials, the Schiff base types, were sensitive to moisture, while the azoxybenzene types were sensitive to light. Therefore, research to improve the stability of liquid crystals to moisture and light had been undertaken. The chemically stable biphenylcarboxylates and cyanobiphenyls were developed one after another. The cyanobiphenyls were found to be exceptional in possessing the necessary properties of display material. They exhibited low viscosity and low voltage operation, leading to many reports on the cyanobiphenyls. The phenylcyclohexane-based liquid crystals also have low viscosity and high response speeds, thus drawing to attention their use as display material. Furthermore, these bicylic liquid crystals were modified by the addition of benzene and cyclohexane rings to produce tricyclic and tetracyclic liquid crystals. As a result, the upper range of temperature was increased. Further improvements in the various physical properties were made by introduction of fluorine and other functional groups to the liquid crystals. The optically active compounds are important components of chiral nematic liquid crystals, chiral smectic liquid crystals, and blue phase. Antiferroelectric liquid crystals of the chiral smectic liquid crystal type are undergoing vigorous synthetic studies to develop novel liquid crystal compounds. Larger high-resolution displays are the target for the next generation of liquid crystal materials. Following are listed building blocks for liquid crystals. These products enable you to develop new liquid crystal materials. A1410

Br

B1304

H0690

Br

C1239

HO

Cl

270

OH

HO

OCH2CH3

CH3(CH2)5O

CN

Br

CH3(CH2)9O

COOH

H0711

CO(CH2)4CH3

CH3(CH2)5

Br

CH3(CH2)4O

HO

O(CH2)4CH3

HOCH2(CH2)5O

Bu

COOH

CH3(CH2)3O

O(CH2)3CH3

H0708

F

H0767

COOH

t

D1082

F0704

CH2CH3

O(CH2)5CH3

CH3(CH2)2

C O

B1986

D1090

E0463

H0710

COOH

CH3(CH2)4

COCH3

B1306

D2041

D1089

H0709

CH3(CH2)6

Br

COCH3 CH3

B1305

H0523

D1127

CH3CH2O

B1866

O

Biphenyls

CH3(CH2)6

A1322

CO(CH2)5CH3

H0819

OCH3

Availability or specification of the listed products are subject to change without prior notice.

CH3O

OH

Building Blocks for Liquid Crystals

H0695

B1924

COOH

P1133

P1212

COCH2CH3

(CH2)4CH3

CO(CH2)6CH3

O(CH2)17CH3

Synthetic Organic Chemistry

HO

O0214

P1037

CH3CH2CH2

COOH

Product Name

A1410 A1322 B1866 B1304 H0690 B1305 B1306 B1986 C1239 H0523 D2041 D1090 D1082 D1127 D1089 E0463 F0704 H0708 H0709 H0710 H0711 H0767 H0819 H0695 B1924 O0214 P1133 P1212 P1037

4-Acetyl-4'-bromobiphenyl 4-Acetyl-4'-methylbiphenyl 4-Biphenyl Benzoate 4-Bromo-4'-heptylbiphenyl 4-Bromo-4'-hydroxybiphenyl 4-Bromo-4'-pentylbiphenyl 4-Bromo-4'-propylbiphenyl 4-(4-tert-Butylphenyl)benzoic Acid 4-Chloro-4'-hydroxybiphenyl 4-Cyano-4'-hydroxybiphenyl 4'-Decyloxybiphenyl-4-carboxylic Acid 4,4'-Diamyloxybiphenyl 4,4'-Dibutoxybiphenyl 4,4'-Diethoxybiphenyl 4,4'-Dihexyloxybiphenyl 4-Ethylbiphenyl 4-Fluoro-4'-hydroxybiphenyl 4-Heptanoylbiphenyl 4-(4-Heptylphenyl)benzoic Acid 4-Hexanoylbiphenyl 4-(4-Hexylphenyl)benzoic Acid 4-(6-Hydroxyhexyloxy)-4'-methoxybiphenyl 4-Hydroxy-4'-methoxybiphenyl 4-(4-Hydroxyphenyl)benzoic Acid 4-Octadecyloxybiphenyl 4-n-Octanoylbiphenyl 4-Pentylbiphenyl 4-Propionylbiphenyl 4-(4-Propylphenyl)benzoic Acid

Materials Chemistry

Product No.

Unit Size 5g 5g 5g 1g 1g 5g

5g

1g 5g

5mL 5g

A0885

A1024

25g 5g 25g 5g 25g 5g 25g 5g 5g 25g 1g 5g 25g 5g 5g 25g 25g 25g 5g 10g 5g 1g 5g 25g 25g 10g 25mL 25g 10g

A0269

COOH

COOH

COOH

OCOCH3

COCH3

NH2

Benzoic Acids

A0741

A0708 COOH

(CH2)4CH3

A0482

B1665

B0553

COOH

COOH

COOH

COOH

O(CH2)4CH3

OCH3

OBn

Br

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

271

Building Blocks for Liquid Crystals

Synthetic Organic Chemistry

B1950

B1585

B0896

COOH

COOH

B0241 COOH

D4176 COOH

COOH

F

OCH2CH2CH

Br

D2859

CH2

E0045

O(CH2)3CH3

E0379

O(CH2)9CH3

(CH2)3CH3

F0337

H0774

COOH

COOH

COOH

COOH

O(CH2)11CH3

OCH2CH3

CH2CH3

O(CH2)7CH3

COOH

Materials Chemistry

F

H0792

H0248 COCl

H0829 COOH

(CH2)6CH3

O(CH2)6CH3

H0642

(CH2)5CH3

H0695

O0137

COOH

272

COOH

O(CH2)5CH3

OH

P0206 COOH

COOH

O(CH2)7CH3

OCH2CH2CH3

COOH

OH

P0945

H0207 COOH

O0117 COOH

HO

O

H0247 COOH

(CH2)6CH3

(CH2)7CH3

T0293

U0072

COOH

COOH

COOH

CH2CH2CH3

CH3

O(CH2)10CH3

Product No.

Product Name

A0885 A1024 A0269 A0741 A0708 A0482 B1665 B0553 B1950 B1585 B0896 B0241 D4176 D2859 E0045 E0379 F0337 H0774 H0792 H0248 H0829 H0247 H0207 H0642

4-Acetoxybenzoic Acid 4-Acetylbenzoic Acid 4-Aminobenzoic Acid 4-Amylbenzoic Acid 4-Amyloxybenzoic Acid p-Anisic Acid 4-Benzyloxybenzoic Acid 4-Bromobenzoic Acid 4-Bromo-2-fluorobenzoic Acid 4-(3-Butenyloxy)benzoic Acid 4-Butoxybenzoic Acid 4-Butylbenzoic Acid 4-(Decyloxy)benzoic Acid 4-(Dodecyloxy)benzoic Acid 4-Ethoxybenzoic Acid 4-Ethylbenzoic Acid 3-Fluoro-4-n-octyloxybenzoic Acid 4-Heptylbenzoic Acid 4-Heptylbenzoyl Chloride 4-(Heptyloxy)benzoic Acid 4-Hexylbenzoic Acid 4-(Hexyloxy)benzoic Acid 4-Hydroxybenzoic Acid 4-(4-Hydroxyphenoxy)benzoic Acid

Unit Size

Availability or specification of the listed products are subject to change without prior notice.

25g 5g

25g

25g 1g 100g 25g 25g 5g 100g 5g

5g 5g 5g

1g 5g 25g

25g

25g 100g 1g

500g 5g 500g 250g 25g 500g 25g 500g 25g 5g 25g 25g 25g 25g 25g 25g 5g 10g 25g 500g 5g 500g 500g 5g

Building Blocks for Liquid Crystals

Product Name

H0695 O0137 O0117 P0206 P0945 T0293 U0072

4-(4-Hydroxyphenyl)benzoic Acid 4-n-Octylbenzoic Acid 4-n-Octyloxybenzoic Acid 4-Propoxybenzoic Acid 4-Propylbenzoic Acid p-Toluic Acid 4-Undecyloxybenzoic Acid

Unit Size 1g

5g 5g

25g 25g

Synthetic Organic Chemistry

Product No.

25g 25g 25g 25g 500g 500g 5g

For others: See our website

References 1992, T. Kitamura, , 72. 1998, H. Numata, , 40. 1995, Y. Suzuki, , 8. 1997, , 9. T. Inukai, K. Miyazawa, G. W. Gray, G. R. Luckhurst, in P. G. Gennes, J. Prost, in

, Academic Press, 1979, pp.1-29, pp.263-284. , Oxford University Press, 1993.

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

Materials Chemistry

1) 2) 3) 4) 5) 6)

273

Materials Chemistry

Synthetic Organic Chemistry

Organic Nonlinear Optical Materials

Organic Nonlinear Optical Materials Advancements of lasers and optical fibers contributed to optical communications and optical disks for practical use. Further development of optical materials is urgently required. Nonlinear optical materials efficiently exhibit nonlinear optical phenomena, which are conversion of light wavelength, amplification of light, and conversion of the refractive index depending on optical intensity. Since a laser oscillation was reported from an inorganic compound in the 1960s, inorganic nonlinear optical materials have been well developed. In addition to these inorganic materials, organic nonlinear optical materials have also been studied. This is because organic materials show efficient nonlinear optical properties and rapid responsiveness based on highly movable π-electrons, thanks to delocalized electrons in organic materials. Nonlinear optical materials may be important for large-capacity communications, because further application of this material may provide a device in an all optical system. As one of the basic technologies of photonics, lightwave technology using organic nonlinear optical effects are important to develop. Further research on organic materials with excellent nonlinear optical properties and vigorous applied studies has been carried out.

A2634

A0621

A1251

A0838

A0794 NO2

CH3

O2 N

NH2

CH3

C0943

NH2

C0214

N

C1209 NH2

O2N N

NH2

N

C1349

NH2

D2020 CH3

NHCH3 Cl

NO2

O 2N

NH2

N(CH3)2

N CH2CN

Cl

O

NH C CH3

Cl NO2

NO2

D2263

D2505

NO2

NO2

D0289

D2135

H0747 O

N

CH3

O

CH3 O2 N

O2N

CH CH

N

CH3

CH3 CH3

H3C

CH3

N H

N H

OCH3 O2N

HN NO2

O 2N

M0997

M0999

M0909

M0985 NO2

CH3 O2N

OCH3

O2N

CH CH

OCH3

N H

M1011 NHCH3

NO2

CH3 N H

N

OH

N NO2

N0529

M1677 NH2

N0527

M0953 NO2

NH2

CH3

274

NHCH3 CH3

CH3

NO2

N0118

NO2

CH3

N O

NO2

Availability or specification of the listed products are subject to change without prior notice.

NH2 NO2

Organic Nonlinear Optical Materials

N0117

N0119

N0400

N0547 CH3

O2N

NO2

N0540

N H

NO2

OH

OH HN

Synthetic Organic Chemistry

NH2

NH2

N0546

HN

N

N NO2

NO2

N0281 OH

N

O O2N

NH

N

N H

O

NO2

Product Name

A2634 A0621 A1251 A0838 A0794 C0943 C0214 C1209 C1349 D2020 D2263 D2505 D0289 D2135 H0747 M0997 M0999 M0909 M0985 M1011 N0529 M1677 N0527 M0953 N0118 N0117 N0119 N0400 N0547 N0546 N0540 N0281

2-Amino-9,9-dimethylfluorene 2-Aminofluorene 4-Amino-4'-nitrobiphenyl 2-Amino-3-nitropyridine 2-Amino-5-nitropyridine 2-Chloro-3,5-dinitropyridine 2-Chloro-4-nitroaniline 2-Chloro-4-nitro-N-methylaniline N-Cyanomethyl-N-methyl-4-nitroaniline 2'-(N,N-Dimethylamino)-5'-nitroacetanilide 4-Dimethylamino-4'-nitrobiphenyl 4-Dimethylamino-4'-nitrostilbene 1,3-Dimethylurea N-(2,4-Dinitrophenyl)-L-alanine Methyl Ester 4-Hydroxy-4'-nitrobiphenyl 4-Methoxy-4'-nitrobiphenyl 4-Methoxy-4'-nitrostilbene (R)-(+)-2-(α-Methylbenzylamino)-5-nitropyridine (S)-(-)-2-(α-Methylbenzylamino)-5-nitropyridine N-Methyl-4-nitroaniline 2-Methyl-4-nitroaniline 3-Methyl-4-nitroaniline 3-Methyl-4-nitropyridine N-Oxide N-Methyl-4-nitro-o-toluidine 2-Nitroaniline 3-Nitroaniline 4-Nitroaniline 5-Nitroindole (S)-(-)-N-(5-Nitro-2-pyridyl)alaninol (S)-N-(5-Nitro-2-pyridyl)phenylalaninol (S)-(-)-N-(5-Nitro-2-pyridyl)prolinol 5-Nitrouracil

Materials Chemistry

Product No.

Unit Size 200mg 5g 1g

1g 25g 5g 5g 25g 250g 1g 5g 25g Price on request 5g 1g 1g 5g 5g 25g 500g 1g 1g 5g 25g 100mg 1g 5g 5g 1g 5g 25g 500g 25g 5g 25g 5g 25g 5g 25g 500g 25g 500g 25g 500g 5g 25g 100mg 1g 1g 5g 5g 25g

References 1) S. Miyata, ., Preprints of IUPAC 32nd International Symposium on Macromolecules, Kyoto, 1988, p.582. 2) D. S. Chemla, J. Zyss, in , Academic Press, New York, 1987. 3) L. M. Hayden, S. T. Kowel, M. P. Srinivasan, . 1987, , 351. 4) C. Flytzanis, J. L. Oudar, in , Springer, Berlin, 1986. 5) P. N. Prasad, D. R. Ulrich, in , Plenum, New York, 1988. 6) D. R. Ulrich, J. Orenstein, A. J. Heeger, in , Material Research Society, Pittsbourgh, 1988.

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

275

Materials Chemistry

Synthetic Organic Chemistry

Materials for Near Infrared Absorption

Materials for Near Infrared Absorption Near infrared dyes show light absorption in the near infrared area of 700-2000 nm. Their intense absorption normally originates from a charge transfer of an organic dye or metal complex. Materials of near infrared absorption involve cyanine dyes having an extended polymethine, phthalocyanine dyes with a metal center of aluminum or zinc, naphthalocyanine dyes, nickel dithiolene complexes with a square-planar geometry, squarylium dyes, quinone analogues, diimonium compounds and azo derivatives. Applications using these organic dyes include security markings, lithography, optical recording media and optical filters. A laser-induced process requires near infrared dyes having a sensitive absorption of longer than 700 nm, high solubility for appropriate organic solvents, and excellent heat-resistivity. In order to increase power conversion efficiency of an organic solar cell, efficient near infrared dyes are required, because sunlight includes near infrared light. Furthermore, near infrared dyes are expected to be biomaterials for chemotherapy and imaging deep-tissue in-vivo by using luminescent phenomena in the near infrared region.

N N

N N

N

+ N

N

N

Cyanine

Phthalocyanine

H2 N

O-

OH S

R

S Ni

S

+ N

N S

R NH2

CH3O

OCH3

CH3

N

n-BuO

S

N

Ni

S

S

S

n-BuO N

OCH3

CH3

CH3

T3204

N

Cu

N

N N

On-Bu N

S N

On-Bu

CH3 CH3 CH CH

S CH CH CH CH CH CH CH

CH2CH3

I

N CH2CH3

N

N

Cl

CH3 CH3 CH CH

CH3

N CH3

CH3

SO3

n-BuO On-Bu

T3205

Cl

Cl S

S

Cl Cl

S

Cl S

Ni

S Ni

S

S

Cl

Cl

S

Cl

(C4H9)4N

276

C2886

N S

CH3O

D4773 n-BuO On-Bu

Ni S

C3051

CH3

S

S

HO

Squarylium

Dithiolene complex

B4361

R R

O

B4360

N

Zn

N

Cl

Cl Cl

(C4H9)4N

Product No.

Product Name

B4360 B4361 C3051 D4773 C2886 T3204 T3205

Bis[4,4'-dimethoxy(dithiobenzil)]nickel(II) Bis(4-dimethylaminodithiobenzil)nickel(II) Copper(II) 5,9,14,18,23,27,32,36-Octabutoxy-2,3-naphthalocyanine 3,3'-Diethylthiatricarbocyanine Iodide IR-813 p-Toluenesulfonate Tetrabutylammonium Bis(3,6-dichloro-1,2-benzenedithiolato)nickelate Tetrabutylammonium Bis(3,4,6-trichloro-1,2-benzenedithiolato)nickelate

Unit Size

Availability or specification of the listed products are subject to change without prior notice.

1g 1g 200mg 1g 1g 5g 1g 5g 200mg 200mg

Magnetic Metal Complexes

Triangular Lattice of Dimer [Pd(dmit)2]2 H0553

H0554 CF3

CF3 O

β-Diketonato Complexes

Co

C0384

Co O CH3

2

. 2H2O

CF3

2

CH3

Mn

. 2H2O

CH3

2

CF3 O Co

V O CH3

. xH2O

O

O 2

. xH2O

T0746

O

O 2

CF3

2

CH3 O

O

Mn O

V0016

Cu

O

. xH2O

Cu O

CH3 O

O

. xH2O

M0042 CH3

CH3

CF3 O

O CF3

C0373 B2681

H0557

2

CH3

2

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

277

Materials Chemistry

Magnetism is mainly classified into five categories: paramagnetism in which unpaired electrons are randomly oriented, ferromagnetism in which unpaired electrons are oriented in the same direction, antiferromagnetism in which unpaired electrons are oriented in antiparallel direction, ferrimagnetism in which unpaired electrons with different magnetic moments are oriented in antiparallel direction, and diamagnetism without unpaired electrons. An application of ferromagnet for electronics is a magnetic disk that is further developed to enhance memory capacity. Many Prussian blue analogues formulated as M4[M(CN)6]3 are ferromagnets and ferrimagnets.1,2) Although neodymium magnets and ferrite magnets are magnetic materials based on inorganic solids, magnetic materials using molecular metal complexes have been also developed. Since a molecular magnetic material has a molecular unit, one advantage is that a chemical modification of the unit molecule controls physical properties. Furthermore, a molecular material can fabricate a device at low cost. Miller . observed a ferromagnet of the charge transfer complex derived from metallocene and tetracyanoethylene (TCNE) or tetracyanoquinodimethane (TCNQ).3,4) Single molecule magnets (SMM) in which a single molecule behaves as a magnet, were intensively investigated from 1993.5,6) The SMM is a specified material obtained from a molecular compound, and the application may be highdensity information media. Single-chain magnets (SCM) are obtained from a one-dimensional assembly of magnetic complexes.7) Kato . reported that physical properties of the metal complex salt of the 1,2-dithiolene ligand formulated as (Cation)[Pd(dmit)2]2 in which the anion radical of the dimer [Pd(dmit)2]2 shows paramagnetism, antiferromagnetism, superconductivity and spin liquid state.8)

Synthetic Organic Chemistry

Magnetic Metal Complexes

Magnetic Metal Complexes

Synthetic Organic Chemistry

T0752

T0685

T1686 CF3

CF3

CH3

CH3

2

M0043

Ph

T0932

CF3

3

O CH3

3

3

T0750

CH3

CF3

CF3 O

O Mn

O Fe

Cr O

O CH3

Cr

O

O 2

O Fe

Fe

O

O

CH3 O

O Mn

Cu

C0336 CF3

Ph

O

O

Materials Chemistry

H0555

CH3

3

O CH3

3

3

Product No.

Product Name

H0553 H0554 H0557 C0373 B2681 C0384 M0042 V0016 T0746 T0752 T0685 T1686 H0555 C0336 M0043 T0932 T0750

Bis(hexafluoroacetylacetonato)cobalt(II) Hydrate Bis(hexafluoroacetylacetonato)copper(II) Hydrate Bis(hexafluoroacetylacetonato)manganese(II) Hydrate Bis(2,4-pentanedionato)cobalt(II) Dihydrate Bis(2,4-pentanedionato)cobalt(II) Bis(2,4-pentanedionato)copper(II) Bis(2,4-pentanedionato)manganese(II) Dihydrate Bis(2,4-pentanedionato)vanadium(IV) Oxide Bis(trifluoro-2,4-pentanedionato)cobalt(II) Hydrate Bis(trifluoro-2,4-pentanedionato)copper(II) Bis(trifluoro-2,4-pentanedionato)manganese(II) Tris(dibenzoylmethanato) Iron Tris(hexafluoroacetylacetonato)iron(III) Tris(2,4-pentanedionato)chromium(III) Tris(2,4-pentanedionato)manganese(III) Tris(trifluoro-2,4-pentanedionato)chromium(III) Tris(trifluoro-2,4-pentanedionato)iron(III)

Unit Size 5g 5g 5g 500g 25g 250g 500g 25g 5g 5g 5g 25g 1g 500g 500g 1g 5g

1g 1g 25g 25g 25g

5g 25g 100g

25g

P0887

C2986

P1005 P1006

N N

Porphyrin & Phthalocyanine Complexes

N N

N

N

N

N

Co

N

N

Co

N N

N N

N Cu

N

N N

N N

T1256

P1628

T1861 OCH3

tBu

N

tBu

N

N

N

N N

N

N

Cu

N

N N

tBu

N N

CH3O

N N

N Co N

OCH3

N OCH3

tBu

278

N Cu

N

Product No.

Product Name

P0887 C2986 P1005 P1006 T1256 P1628

Cobalt(II) Phthalocyanine Cobalt(II) Tetraphenylporphyrin Copper(II) Phthalocyanine (α-form) Copper(II) Phthalocyanine (β-form) Copper(II) 2,9,16,23-Tetra-tert-butylphthalocyanine Pigment Blue 15 (purified by sublimation)

Unit Size

Availability or specification of the listed products are subject to change without prior notice.

1g 25g 25g

25g 5g 250g 500g 100mg 1g

Magnetic Metal Complexes

Product Name

T1861

[5,10,15,20-Tetrakis(4-methoxyphenyl)porphyrinato]cobalt(II)

Unit Size

B4360

1g

B4361

CH3O

OCH3 S

Dithiolene Complexes

B1350

CH3

N

S

S

S

S

S

S

S Ni

Ni

CH3O

5g

CH3

Ni S

Synthetic Organic Chemistry

Product No.

S N

OCH3

S

CH3

S

CH3

B1438

B1371

D2134

T3204 Cl

S

S

S

S

S

S

S

S

S

2

Pd

S

S

S

S

S

S

S

S

S

2

Pt

S

S

NC

S

S

CN

S

CN

Cl

2

Ni

S

2 (C4H9)4N

2 (C4H9)4N

NC

S

S

S

S

S

S

S

S

S

S

Au

S Ni

S

S

(C18H37)2(CH3)2N

2 (C4H9)4N

Materials Chemistry

B1437

S

Cl

Cl (C4H9)4N

T1272

T1415

S

S

S

S

S

S

S

S

NC

Ni

S

T3205 S

NC

(C4H9)4N

CN

S

Cl

S

Cl S

Ni

S

T1416

Cl S Ni

S

S

CN

Cl

Cl

(C4H9)4N

S

S

S

S

S

S

S

S

S

S

Ni

S

(C4H9)4P

Cl (C4H9)4N

Product No.

Product Name

B4360 B4361 B1350 B1437 B1438 B1371 D2134 T3204 T1272 T1415 T3205 T1416

Bis[4,4'-dimethoxy(dithiobenzil)]nickel(II) Bis(4-dimethylaminodithiobenzil)nickel(II) Bis(dithiobenzil)nickel(II) Bis(tetrabutylammonium) Bis(1,3-dithiole-2-thione-4,5-dithiolato)palladium(II) Bis(tetrabutylammonium) Bis(1,3-dithiole-2-thione-4,5-dithiolato)platinum(II) Bis(tetrabutylammonium) Bis(maleonitriledithiolato)nickel(II) Complex Dioctadecyldimethylammonium Bis(1,3-dithiole-2-thione-4,5-dithiolato)aurate(III) Tetrabutylammonium Bis(3,6-dichloro-1,2-benzenedithiolato)nickelate Tetrabutylammonium Bis(1,3-dithiole-2-thione-4,5-dithiolato)nickel(III) Complex Tetrabutylammonium Bis(maleonitriledithiolato)nickel(III) Complex Tetrabutylammonium Bis(3,4,6-trichloro-1,2-benzenedithiolato)nickelate Tetrabutylphosphonium Bis(1,3-dithiole-2-thione-4,5-dithiolato)nickel(III) Complex

Unit Size

B0491

1g 1g 1g 100mg 1g 100mg 1g 100mg 200mg 100mg 1g 200mg 1g

D0487

D1022 S

HOCH2CH2

Dithiocarbamato Complexes

D0489

CH3

2

CH3 CH3

N

S

Cu2 2

CH3

N

Cu2

S

CH3

2

D1267 S

CH3

Cu2+

N C S HOCH2CH2

S

S

N

S S

Fe 3 3

CH3

N CH3

S

Fe 3 3

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

279

Materials Chemistry

Synthetic Organic Chemistry

Magnetic Metal Complexes

Product No.

Product Name

B0491 D0487 D1022 D0489 D1267

Copper(II) Bis(2-hydroxyethyl)dithiocarbamate Copper Diethyldithiocarbamate Copper(II) Dimethyldithiocarbamate Iron(III) Diethyldithiocarbamate Iron(III) Dimethyldithiocarbamate

Unit Size

25g

P1347

B3834 B1677 N

Other Complexes

I0849

O Cu O

25g 25g 25g 25g 500g

C2346

O

O N

N

C O

Cr3

Cu2

CH3 C O

2

3

. H2O

S0318

N

Fe 4[Fe(CN)6]3

N Co

O

O

Product No.

Product Name

B3834 B1677 P1347 C2346 I0849 S0318

Bis(8-quinolinolato)copper(II) (purified by sublimation) Bis(8-quinolinolato)copper(II) Chromium(III) Pyridine-2-carboxylate Copper(II) Acetate Monohydrate Iron(III) Hexacyanoferrate(II) Salcomine [=N,N '-Bis(salicylidene)ethylenediiminocobalt(II)]

Unit Size

25g 25g

100g

1g 25g 25g 500g 25g 500g

References 1) 2) 3) 4) 5) 6) 7) 8)

280

S. Ohkoshi, H. Tokoro, T. Matsuda, H. Takahashi, H. Irie, K. Hashimoto, . 2007, , 3238. W. Kosaka, K. Nomura, K. Hashimoto, S. Ohkoshi, . 2005, , 8590. J. S. Miller, A. J. Epstein, . 1994, , 385. J. S. Miller, D. A. Dixon, R. S. McLean, D. M. Groski, R. B. Flippen, J. M. Manriquez, G. T. Yee, K. S. Narayan, A. J. Epstein, . 1991, , 309. 1993, R. Sessoli, D. Gatteschi, A. Caneschi, M. A. Novak, , 141. T. Komeda, H. Isshiki, J. Liu, Y.-F. Zhang, N. Lorente, K. Katoh, B. K. Breedlove, M. Yamashita, . 2011, , 1210. R. Clérac, H. Miyasaka, M. Yamashita, C. Coulon, . 2002, , 12837. Review: R. Kato, . 2014, , 355.

Availability or specification of the listed products are subject to change without prior notice.

Organic Radicals

O

O2N

N

CH3 CH3

CH3

N

CH3

CH3

O2N O

O

CH3

N

N

CH3

N

H0878

NO2

CH3

CH3

CH3

O

CH3 N

CH3

M1197

N O

CH3

N O2N N O

CH3 CH3 CH3 CH3

O

CH3

C(CH3)3

CH3

CH

O

O

O

O CH3

NCS

O C C CH2 CH3

CH3 CH3

I

CH3

CH3

N

CH3

O

O CH3

N O

CH3

CH3

CH3 N

CH3

T1560

N CH3

CH3 O

A5440 O

CH3

CH3

M1531

O

N

CH3 N O

O0266 O

CH3

.O

C(CH3)3

(CH3)3C

O

D2295 OCH3

CH2CH3

O

CH3

CH3

H0865

I0486

CH3

CH3 N O

(CH3)3C

(CH2)14 C OH

I0908

O

CH3

N

O

CH3

CH3

OH

O

O

CH3

HN C CH2I

CH3

CH3

O

O

I0487 O

N

CH3

CH3 N

G0020

O 2N

O C

CH3

D2399

CH3

HN C CH2Cl

C OH CH3

O

N N

CH3

O

CH3

N

O

O

CH3

O 2N CH3

CH3

CH3

CH3

D4313

CH3

CH3

CH3

O

CN

C1432

C OH CH3

O

C1782

C1406 O

CH3

CH3

DPPH [D4313]

[T1560]

NH2

CH3

NO2

O2N

C1428

HN C CH3 CH3

N N

CH3

TEMPO

A1343 O

CH3

N

CH3

NPNN [D2295]

A1348

CH3

N O

CH3 CH3 CH3 CH3

CH3 CH3

CH3 N

CH3

O

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

281

Materials Chemistry

Ferromagnetic and ferrimagnetic properties of metal compounds are based on contributions of unpaired d- or f-electrons of transition or lanthanoid metals. On the other hand, magnetic properties of metal-free organic compounds are due to unpaired π-electrons. Normally, π-electrons are favorable to electrical conduction in material science, because they are movable by the π-conjugation effect, but they have received less attention for magnetic materials. However, diverse chemical modifications of an organic molecule have produced organic radical-based ferromagnets.1,2) It is known that the charge transfer complex obtained from fullerene with tetrakis(dimethylamino)ethylene (TDAE) becomes an organic magnet.3) In addition to using a π-conjugated organic radical, localized free radical species also provide organic magnets. 4-Nitrophenylnitronyl nitroxide (NPNN) was the first organic ferromagnet in a pure organic radical.4) Nogami . reported that 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) and its analogues became ferromagnets or antiferromagnets.5,6) Furthermore, 1,1-diphenyl-2-picrylhydrazyl (DPPH) is an antiferromagnet at extremely low temperature.

Synthetic Organic Chemistry

Organic Radicals

Materials Chemistry

Synthetic Organic Chemistry

Organic Radicals

Product No.

Product Name

A1348 A1343 C1428 C1406 C1432 C1782 D4313 D2399 G0020 H0865 H0878 I0487 I0908 I0486 M1531 M1197 D2295 O0266 A5440 T1560

4-Acetamido-2,2,6,6-tetramethylpiperidine 1-Oxyl Free Radical 4-Amino-2,2,6,6-tetramethylpiperidine 1-Oxyl Free Radical 4-Carboxy-2,2,6,6-tetramethylpiperidine 1-Oxyl Free Radical 3-Carboxy-2,2,5,5-tetramethylpyrrolidine 1-Oxyl Free Radical 4-(2-Chloroacetamido)-2,2,6,6-tetramethylpiperidine 1-Oxyl Free Radical 4-Cyano-2,2,6,6-tetramethylpiperidine 1-Oxyl Free Radical 1,1-Diphenyl-2-picrylhydrazyl Free Radical 16-DOXYL-stearic Acid Free Radical Galvinoxyl Free Radical 4-Hydroxy-2,2,6,6-tetramethylpiperidine 1-Oxyl Free Radical 4-Hydroxy-2,2,6,6-tetramethylpiperidine 1-Oxyl Benzoate Free Radical 4-(2-Iodoacetamido)-2,2,6,6-tetramethylpiperidine 1-Oxyl Free Radical 4-[2-[2-(4-Iodophenoxy)ethoxy]carbonyl]benzoyloxy-2,2,6,6-tetramethylpiperidin-1-oxyl 4-Isothiocyanato-2,2,6,6-tetramethylpiperidine 1-Oxyl Free Radical 4-Methacryloyloxy-2,2,6,6-tetramethylpiperidine 1-Oxyl Free Radical 4-Methoxy-2,2,6,6-tetramethylpiperidine 1-Oxyl Free Radical 2-(4-Nitrophenyl)-4,4,5,5-tetramethylimidazoline-3-oxide-1-oxyl Free Radical 4-Oxo-2,2,6,6-tetramethylpiperidine 1-Oxyl Free Radical PTIO (=2-Phenyl-4,4,5,5-tetramethylimidazoline-3-oxide-1-oxyl) 2,2,6,6-Tetramethylpiperidine 1-Oxyl Free Radical

Unit Size 5g 1g 100mg 100mg 1g 25mg 1g 5g 1g

100mg 1g 1g 5g 1g 5g

25g 5g 1g 1g 1g 1g 5g 100mg 5g 25g 5g 100mg 100mg 1g 5g 5g 100mg 25g 5g 25g

References 2001, 1) W. Fujita, K. Awaga, , 3601. 2) W. Fujita, K. Awaga, . 2002, , 385. 3) P. W. Stephens, D. Cox, J. W. Lauher, L. Mihaly, J. B. Wiley, P.-M. Allemand, A. Hirsch, K. Holczer, Q. Li, J. D. Thompson, F. 1992, Wudl, , 331. 4) M. Kinoshita, P. Turek, M. Tamura, K. Nozawa, D. Shiomi, Y. Nakazawa, M. Ishikawa, M. Takahashi, K. Awaga, T. Inabe, Y. Maruyama, . 1991, , 1225. 5) T. Nogami, K. Tomioka, T. Ishida, H. Yoshikawa, M. Yasui, F. Iwasaki, H. Iwamura, N. Takeda, M. Ishikawa, . 1994, , 29. 6) T. Nogami, T. Ishida, M. Yasui, F. Iwasaki, N. Takeda, M. Ishikawa, T. Kawakami, K. Yamaguchi, . 1996, , 1841.

282

Availability or specification of the listed products are subject to change without prior notice.

Magnetic Ionic Liquids

N

CH3 FeCl4

N

(CH2)3CH3

[B2672]

B2672

B2672 + Water

B2672

Water

Neodymium magnet

E0706 N

CH3

N

N

FeCl4

(CH2)3CH3

CH3

N

FeCl4

CH2CH3

Product No.

Product Name

B2672 E0706

1-Butyl-3-methylimidazolium Tetrachloroferrate 1-Ethyl-3-methylimidazolium Tetrachloroferrate

Unit Size 5g

25g 5g

References 1) S. Hayashi, H. Hamaguchi, . 2004, 2) K. Iwata, H. Okajima, S. Saha, H. Hamaguchi,

, 1590.

. 2007,

, 1174.

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

283

Materials Chemistry

Ionic liquids consist of only ionic components, having high ionic conductivity suitable for a liquid electrolyte. An electrolyte for a secondary battery requires not only high ionic conductivity but also nonvolatility, heat-resistivity, non-inflammability, and non-corrosiveness. Ionic liquids cover these conditions. The cationic component of ionic liquid involves alkyl-substituted imidazolium, pyrrolidinium, piperidinium, ammonium, phosphonium, sulfonium and the anionic component involves halide, BF4, PF6, thiocyanate, and di(sulfonyl)imide. Chemical modifications of the cation and anion control melting point, viscosity and ionic conductivity. Hamaguchi . observed magnetic ionic liquids by introducing FeCl4 to the anion part to form 1-butyl-3-methylimidazolium tetrachloroferrate, (Bmim)FeCl4.1,2) A magnetic fluid is a liquid with magnetic properties. However, a conventional magnetic fluid contains volatile solvents. It causes a change of viscosity and phase separation by cohesion/precipitation. On the other hand, the magnetic ionic liquid is a highly stable and non-volatile liquid. Moreover, this magnetic ionic liquid responds to a magnetic field by a permanent magnet, because it shows large magnetic susceptibility at room temperature.

Synthetic Organic Chemistry

Magnetic Ionic Liquids

Synthetic Organic Chemistry

Coumarin Dyes

Coumarin Dyes Coumarins are aromatic lactone compounds and many of them exist in natural plants. A coumarin compound with an electron-donating group on the 7-position shows strong light absorption and luminescence, whereas unsubstituted coumarin compounds are hardly luminescent. This is because intramolecular charge transfer occurs when electron-donating and -withdrawing groups coexist in the coumarin molecule. An introduction of a group on the 3- or 4-position largely controls the wavelength of light absorption and luminescence. Furthermore, an introduction of an electron-withdrawing group on these positions can enhance the intensity of luminescence. Such coumarin dyes are useful for laser dyes emitting blue-green light.

Materials Chemistry

5

4

6

3

7

O 2 O

8

B2111

B2088

1

C2267

C2858

C2268

CH3 N

CH3CH2

O

C OCH2CH3 S

N

O

Et2N

CH2CH3

C3044

O

O

C3072

O

O

O

O

O

C3045 O O

O

N

O

O

O

N

O

O

D4462

D4238

CH3CH2 CH3CH2

CH3 CH3

M0631

N

O

O

D4466

CH3CH2 CH3CH2

N

O

O

C OH CH3CH2

N

CH3CH2

D3355

CH3

N

O

CN

O

CH3

O

CH3 CH3

S

CH3 CH3

O

N

N

C2837

N

O

CH3 CH3

D3354

CH3 CH3

O

O

O N

O

CH3 N

N

N

B4257 O

CH3 CH3

O

C2836

N N

C3046

O

C3047

SO2CH3 N

O

N N H

N

CF3

O

O

D3356 CF3

CH3

CF3

N CH3CH2

N

O

O

CH3

CH3CH2

CH2CH3

CH3CH2

E1132

N

O

O

E1129

CH3CH2 CH3CH2

N

O

E0642

CH3

CH3

284

N

O

O

C OCH2CH3

O

O

CH3

N H

O

O

CH3CH2

N

O

O

O

C O(CH2)5CH3 CH3CH2 CH3CH2

CH3

N CH3

O

CH3CH2

N H

CH3 CH3

H1145

CH3 CH3

O

N

O

O

Availability or specification of the listed products are subject to change without prior notice.

O

O

Coumarin Dyes

3-(2-Benzimidazolyl)-7-(diethylamino)coumarin 3-(2-Benzothiazolyl)-7-(diethylamino)coumarin Coumarin 102 Coumarin 153 Coumarin 314 Coumarin 498 Coumarin 510 Coumarin 525 Coumarin 6H Coumarin 504T Coumarin 521T Coumarin 545T 7-(Diethylamino)coumarin 7-(Diethylamino)coumarin-3-carbonitrile 7-(Diethylamino)coumarin-3-carboxylic Acid 7-(Diethylamino)-3-(1-methyl-2-benzimidazolyl)coumarin 7-Diethylamino-4-methylcoumarin 7-(Diethylamino)-4-(trifluoromethyl)coumarin 7-(Dimethylamino)-4-methylcoumarin 7-(Dimethylamino)-4-(trifluoromethyl)coumarin 7-(Ethylamino)-4,6-dimethylcoumarin 7-(Ethylamino)-4-methylcoumarin Ethyl 7-(Diethylamino)coumarin-3-carboxylate Hexyl 7-(Diethylamino)coumarin-3-carboxylate

Unit Size 100mg 1g 200mg

200mg 200mg 200mg

200mg 1g 200mg 25g 5g 5g 200mg 1g 1g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

1g 5g 1g 1g 1g 200mg 1g 200mg 1g 1g 200mg 200mg 1g 5g 100mg 1g 500g 200mg 25g 25g 1g 200mg 5g 5g

Materials Chemistry

Product Name

B2111 B2088 C2267 C2858 C2268 C3044 C3072 C3047 C2836 C3045 C3046 B4257 D3354 D4462 D4238 C2837 M0631 D4466 D3355 D3356 E1132 E1129 E0642 H1145

Synthetic Organic Chemistry

Product No.

285

Materials Chemistry

Synthetic Organic Chemistry

Porphyrin & Phthalocyanine Dyes

Porphyrin & Phthalocyanine Dyes Porphyrin has a cyclic structure with four condensed pyrroles. The corresponding porphyrin metal complexes are important in-vivo, because they are included in chlorophyll functioning photo absorption and photo electron transfer for photosynthesis, and also included in heme (hemoglobin) transporting oxygen in blood. In addition, porphyrinato metal complexes are useful for photoelectron functional materials, metal complex catalysts and molecular electrical conductors. Chemical modifications of substituted groups, metal centers, and axial ligands on the porphyrinato metal complexes show various functionalities. Normal porphyrin complexes have sharp absorptions, the so-called Soret band, around 400-500 nm, and the Q band around 500-700 nm that is a relatively weak absorption. Molar absorption coefficients of the Soret band are up to order of 106 M/cm. The chlorophyll and porphyrinato zinc complexes hardly show energy relaxation of absorbed light, but easily show photoelectron transfer. Therefore, studies on porphyrinato metal complexes are performed for artificial photosynthesis (eg. reduction of carbon dioxide) and solar cell materials.

N NH

NH

N

N N

N HN

N

HN

N N

Porphyrin

Phthalocyanine

Phthalocyanine compounds do not exist in nature, although they have an analogue structure to porphyrin compounds. The phthalocyanato metal complexes are artificial dyes for painting of railway trains, and for organic photoconductors of electrophotography. There are applications of organic semiconductors as organic transistors and hole injection materials for organic light-emitting diodes (OLED). The phthalocyanato metal complexes show a more intense Q band absorption than that of the Soret band. Their absorption wavelengths are shifted to longer wavelengths than those of porphyrin compounds. Absorption wavelength is further shifted to the near infrared area by modification of the central metal and expansion of the π-conjugates. Introduction of an alkyl group provides soluble phthalocyanine and porphyrin compounds, although they are poorly soluble due to the large π-conjugated cycle. C1630

P0887

C2986

C3051

C2427

N NH N

N

O C OH

N HN

N

N

N

Co

N

N

Co

n-BuO

N

N

N

n-BuO

Cu

N

On-Bu

N

N

N

N

N

P1049

N N

Cu N

On-Bu

N N

F

n-BuO On-Bu

T1256

F

F

D2860

F

P0973

tBu

N

tBu

N N

N

N

N

F N N N

F

F

N

N

N Na2

N

N

N

HN

N

N

P0766

P1018

F

N

N N

N

F

Fe N

F

F

N

N

N

N N

F

M2209 N

N

N

N F

N N

N

N

tBu

F

N Cu

F

Li2 N

I0783 P0774

F

F N

F

NH

N

tBu

H1194 F

N N

N

F

N

N

Cu

N

N

N

N

N

Cu N

N

N

N

286

N

F

N

N

N

P1005 P1006

F

F

N

N

N

F

n-BuO On-Bu

N

N N

Pb N

N N

N

N

N Mg

N

N N

N

Availability or specification of the listed products are subject to change without prior notice.

N Mg

N

N

N

Porphyrin & Phthalocyanine Dyes

M1338

O0234

O0319 CH2CH3

N

C OCH3

HN

N

NH

O

N

HN

F

FF

CH2CH3

CH3CH2

FF

F

F

N

N

N

Cl

Cl

Cl

Cl NH

OH

CH3O

NH

OCH3

N

OH

NH

HO

CH3O

N

OH

N HN

OCH3

Cl

T1861

CH3O

OH

T1730 F

F

N Co N N

OCH3

NH

N

N HN

F F

OCH3

T2222

F

F F

F F

F

OCH3

T1358 CH3 H3C

F

F

F F

OH

CH3

F

F F

N

OCH3

T1729

OCH3

OCH3

T1359

OCH3

N HN

HO

N HN

OH

N

HO

Cl Cl

CH3O

T1497 CH3O

OH

NH

OR

OCH3

NH2

N HN

HN

Cl

NH N

NH2

N HN

N

T1832

HO

N

N

R = CH2CO2H

NH N

H2N

N N

Cl

Cl

OR

N Ag2

N

Cl

T1815 Cl

N N

Cl

Cl

HO

T1360

Cl

N N

Materials Chemistry

T1438

N HN

N

Cl

OR

N

NH2

Cl Cl

N

T1494

N

N

HN

N Al N Cl N

Cl

N Cu

N

Cl

N

N

N

Cl

N N

N

N

NH N

N

Cl

N

N N

N

Cu N

NH N

F

F

N

S0363

Cl

N

T1495

N

FF

Cl

N Cl N Si N Cl N

CH3O

F F

N HN FF

FF

P0660

N

RO

N

F F NH N

CH2CH3

P1628 P0655

N

FF

F

N CH3CH2

P0996

F

C1167

P1795 P0355

F

F F

CH2CH3

CH3CH2 NH

F

F

Synthetic Organic Chemistry

CH3CH2

F

CH3 H3C CH3

CH3 CH3

NH N N HN

F

F

NH

CH3

N

CH3

N HN

CH3 CH3

T2940

P1024

P0997

N

N

N NH N

N

NH N

HN

N

N

N

N

HN

N Cl N Sn N Cl N N

N N

N

N N

Sn N

N N

N

N

N Cl N Sn N Cl N

N

N

N

T2272

P0767

Z0036

N

N

N O N Ti N N

N N

N

N

N N

Zn N

N

N N

Zn

N N

N

N

Product No.

Product Name

C1630 P0887 C2986 C3051 C2427 P1005 P1006 T1256 P1049 D2860 P0973 H1194

5-(4-Carboxyphenyl)-10,15,20-triphenylporphyrin Cobalt(II) Phthalocyanine Cobalt(II) Tetraphenylporphyrin Copper(II) 5,9,14,18,23,27,32,36-Octabutoxy-2,3-naphthalocyanine Copper(II) 2,3,9,10,16,17,23,24-Octafluorophthalocyanine (purified by sublimation) Copper(II) Phthalocyanine (α-form) Copper(II) Phthalocyanine (β-form) Copper(II) 2,9,16,23-Tetra-tert-butylphthalocyanine Dilithium Phthalocyanine 5,15-Diphenylporphyrin Disodium Phthalocyanine 1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-Hexadecafluorophthalocyanine Copper(II)

I0783 P0774

Iron(II) Phthalocyanine (purified by sublimation) Iron(II) Phthalocyanine

(purified by sublimation)

Unit Size 1g 200mg 100mg 25g 25g

1g 100mg 200mg

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

100mg 25g 5g 1g 1g 250g 500g 100mg 1g 100mg 5g 1g 1g 25g

287

Materials Chemistry

Synthetic Organic Chemistry

Porphyrin & Phthalocyanine Dyes

288

Product No.

Product Name

P0766 P1018 M2209 M1338 O0234 O0319 P1795 P0355 C1167 P0996 P1628 P0655 P0660 S0363 T1494 T1495 T1438 T1815 T1832 T1497 T1360 T1861 T1730 T1729 T1358 T1359 T2222 T2940 P1024 P0997 T2272 P0767 Z0036

Lead(II) Phthalocyanine Magnesium(II) Phthalocyanine Magnesium Porphyrin 5-(4-Methoxycarbonylphenyl)-10,15,20-triphenylporphyrin 2,3,7,8,12,13,17,18-Octaethylporphyrin 2,3,7,8,12,13,17,18-Octafluoro-5,10,15,20-tetrakis(pentafluorophenyl)porphyrin Phthalocyanine (purified by sublimation) Phthalocyanine Phthalocyanine Chloroaluminum Phthalocyanine Silicon Dichloride Pigment Blue 15 (purified by sublimation) Pigment Blue 15 Pigment Green 7 Silver(I) Phthalocyanine 5,10,15,20-Tetrakis(4-aminophenyl)porphyrin 5,10,15,20-Tetrakis(4-carboxymethyloxyphenyl)porphyrin 5,10,15,20-Tetrakis(2,6-dichlorophenyl)porphyrin 5,10,15,20-Tetrakis(3,5-dihydroxyphenyl)porphyrin 5,10,15,20-Tetrakis(3,5-dimethoxyphenyl)porphyrin 5,10,15,20-Tetrakis(4-hydroxyphenyl)porphyrin 5,10,15,20-Tetrakis(4-methoxyphenyl)porphyrin [5,10,15,20-Tetrakis(4-methoxyphenyl)porphyrinato]cobalt(II) 5,10,15,20-Tetrakis(pentafluorophenyl)porphyrin 5,10,15,20-Tetrakis(2,4,6-trimethylphenyl)porphyrin meso-Tetraphenylchlorin Tetraphenylporphyrin (Chlorin free) 5,10,15,20-Tetra(4-pyridyl)porphyrin Tin(IV) 2,3-Naphthalocyanine Dichloride Tin(II) Phthalocyanine Tin(IV) Phthalocyanine Dichloride Titanyl Phthalocyanine (purified by sublimation) Zinc Phthalocyanine Zinc(II) Tetraphenylporphyrin

Unit Size

Availability or specification of the listed products are subject to change without prior notice.

1g

25g 1g 100mg 100mg 1g 100mg 1g 100mg 1g 25g 1g Price on request 1g 25g 25g Price on request 100mg 100mg 100mg 100mg 1g 100mg 100mg 100mg 1g 1g 5g 100mg 100mg 1g 100mg 1g 1g 200mg 1g 1g 5g 1g 200mg 1g 1g 10g 25g 1g 5g

Perylene Dyes

O

O

O

O Imidation

O

O

2

1

12

11

3

O

10

R N

O

O

N R 4

9 5

[P0972]

6

7

Alkylation or Halogenation

1

X

4

9

1

12 11

O

5

6

X

O

4

9

O B O

8

2

O

N R 7

O

Sonogashira coupling (X = halogen)

R N 6

8

R

10

5

7

B O

3

O

O N R

O

2

O

11 10

Boronation

O O B

12

3

R N

O

8

2

O

1

12

11

3

10

4

9

R N

O

N R

O

B O

O

5

6

7

8

O

O R

B4268

B4394

(CH3)2CH O

O CH(CH3)2

N

O O

N

O CH(CH3)2

B2892

CH3O

(CH3)2CH O

N

(CH3)2CH O

B4231

(CH3)2CH O

O CH(CH3)2

O O

O CH(CH3)2

O

N

N

O

O

OCH3

CH3(CH2)7

O

O

N

N

CH3

CH3(CH2)3CHCH2 N

O

O

CH2CH3

N

D4175

O

CH3

B4343

CH3

O

CH3

D3947

O

O

N

N (CH2)7CH3

O

O

O

O

CH2CH3

N CH2CH(CH2)3CH3 O

P0972

O CH3(CH2)12 N O

O

O

O

O

O

O

O N (CH2)12CH3 O

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

289

Materials Chemistry

Perylene was a p-type organic semiconductor and it was known in the 1950s that the brominedoped material showed electrical conductivity1). In contrast to that, perylenetetracarboxylic dianhydride and perylenetetracarboxylic diimide derivatives are n-type organic semiconductors. The latter perylenetetracarboxylic derivatives (PDI or PBI) are important semiconducting materials, because n-type ones are relatively less known than p-type ones. In fact, PTCBI (3,4,9,10-perylenetetracarboxylic bisbenzimidazole) was an n-type organic semiconductor for a prototype of organic photovoltaics.2) Applications in organic electronics using PDI derivatives are organic light-emitting diode (OLED) materials3) and laser dyes4) thanks to their high fluorescent quantum efficiency and photochemical stability. PDIs with electron mobility larger than 0.1 cm2/Vs are also reported.5,6) An introduction of an alkyl group on the imido moiety (NR) produces soluble PDI derivatives, although they are poorly soluble in general.7) Recent research has proved direct alkylations at the meta positions (1,6,7,12-positions),8,9) and direct boronations at the ortho positions (2,5,8,11-positions)10) for PDIs. Halogenations at the meta positions are available, followed by various cross-coupling reactions11) and polymerizations12) providing PDI derivatives with diverse molecular structures and molecular weights.

Synthetic Organic Chemistry

Perylene Dyes

Perylene Dyes

Synthetic Organic Chemistry

P0984 O

P2119 O

HN

NH

T3061 N

N

N

N

O

O

N

N

N

N

O

(CH3)2CH O

(CH3)3C

O CH(CH3)2 N

O O

O CH(CH3)2

C(CH3)3

Product No.

Product Name

B4268 B4394

N,N '-Bis(2,6-diisopropylphenyl)-3,4,9,10-perylenetetracarboxylic Diimide 1g 5g N,N '-Bis(2,6-diisopropylphenyl)-1,6,7,12-tetraphenoxy-3,4,9,10-perylenetetracarboxylic Diimide 1g 5g N,N '-Bis(3,5-dimethylphenyl)-3,4,9,10-perylenetetracarboxylic Diimide 1g 5g N,N '-Bis(2-ethylhexyl)-3,4,9,10-perylenetetracarboxylic Diimide 200mg N,N '-Bis(4-methoxyphenyl)-3,4,9,10-perylenetetracarboxylic Diimide 1g 5g N,N '-Di-n-octyl-3,4,9,10-perylenetetracarboxylic Diimide 1g N,N '-Ditridecyl-3,4,9,10-perylenetetracarboxylic Diimide 200mg 1g 3,4,9,10-Perylenetetracarboxylic Dianhydride 25g 100g 500g 3,4,9,10-Perylenetetracarboxylic Diimide 25g 200mg PTCBI (cis- and trans- mixture) 1,6,7,12-Tetrakis(4-tert-butylphenoxy)-N,N '-bis(2,6-diisopropylphenyl)3,4,9,10-perylenetetracarboxylic Diimide 200mg

B4231 B4343 B2892 D4175 D3947 P0972 P0984 P2119 T3061

Materials Chemistry

(CH3)2CH O

C(CH3)3

O O

N

O

O

O

(CH3)3C

Unit Size

References 1) 2) 3) 4) 5) 6) 7) 8) 9) 10) 11) 12)

290

1954, H. Akamasu, H. Inokuchi, Y. Matsunaga, , 168. C. W. Tang, . 1986, , 183. P. Ranke, I. Bleyl, J. Simmerer, D. Haarer, A. Bacher, H. W. Schmidt, . 1997, , 1332. M. G. Ramirez, M. Morales-Vidal, V. Navarro-Fuster, P. G. Boj, J. A. Quintana, J. M. Villalvilla, A. Retolaza, S. Merino, M. A. 2013, , 1182. Diaz-Garcia, P. R. L. Malenfant, C. D. Dimitrakopoulos, J. D. Gelorme, L. L. Kosbar, T. O. Graham, A. Curioni, W. Andreoni, . 2002, , 2517. R. J. Chesterfield, J. C. McKeen, C. R. Newman, P. C. Ewbank, D. A. da Silva Filho, J.-L. Brédas, L. L. Miller, K. R. Mann, 2004, C. D. Frisbie, , 19281. R. Narayan, P. Kumar, K. S. Narayan, S. K. Asha, . 2013, , 2033. W. Yue, Y. Li, W. Jiang, Y. Zhen, Z. Wang, . 2009, , 5430. Y. Li, C. Li, W. Yue, W. Jiang, R. Kopecek, J. Qu, Z. Wang, . 2010, , 2374. G. Battagliarin, C. Li, V. Enkelmann, K. Müllen, . 2011, , 3012. J. Sun, F. Zhong, J. Zhao, . 2013, , 9595. 2012, X. Hu, L. Zuo, H. Pan, F. Hao, J. Pan, L. Fu, M. Shi, H. Chen, , 157.

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

Cyanine & Squarylium Dyes

N

n

n = 1: cyanine n = 2: carbocyanine n = 3: dicarbocyanine n = 4: tricarbocyanine

N

X

Squarylium dye (SQ), which is an analogue of cyanine dye, has a squaraine moiety in the center of the π-conjugate. The SQ dye has a zwitterion structure in which the cation and anion coexist in the molecule, although the cyanine dye has a separated cation component. The SQ was conventionally used as a charge generation material for an organic photo conductors.6,7) Recently, SQ provided a sensitizer for organic solar cells originating from a strong absorption in near infrared area.8,9) In addition, the SQ dye was applied to an organic light-emitting diode because it shows efficient red luminescence.10)

OH

OH

O

N

N O

N

N O

HO

[B4342]

B4342 OH

O

C0426

CH3 CH3 OH

HO

HO

[B4649]

B4649

CH3

O

O

C0436

CH3

CH3 HO

CHCH

CH

N

N

CH3 N

N

2+

CH3

CH3

N

I

N

2+

O

CH3 CH3

D4453

O

CH3CH2

CH3

N

O CH CH CH

CH2CH3

I

CH2CH3

A2684

O N

CH2CH3

CH2CH3

CH CH CH CH CH I

N

CH3 CH3

I

D4454

O

N

N CH3

CH3

D4457 O

CH3

N CH2CH3

N

CH3

CH3

CH3

CH3

CH CH CH

CH2CH3

I

S

S

N

N

CH2CH3

CH2CH3

CH CH CH I

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

N CH2CH3

291

Materials Chemistry

Cyanine dyes contain some -heterocycles on both sides of the polymethine structure. The -heterocycle on the one side is a cationic ammonium with an electron-withdrawing effect, and the other -heterocycle is a tertiary amine with an electron-donating effect. Accordingly, cyanine dyes show the light absorption of a charge transfer through the central polymethine structure. An extension of the polymethine structure exhibits a red shift of absorption. The absorption of cyanine dyes shifts to longer wavelengths with every extension by the addition of two methine moieties (or by the addition of one moiety).1) There are cyanine dyes exhibiting near infrared absorption. The -heterocycles contained in the cyanine dyes consist of indole, benzoxazole, benzothiazole, naphthothiazole, quinoline and so on. Proper selection of these -heterocycles controls absorption wavelength. Increasing the number of aromatic rings shifts absorption to longer wavelengths. Counter anions consist of halides, sulfonate, perchlorate, tetrafluoroborate, hexafluoroantimonate and so on. Proper selection of these anions enhances solubility and durability.2,3) Cyanine dyes are useful for silver photography, and optical recording media by laser sensitivity.4) Water-soluble cyanine dyes are usable as fluorescent probes in biochemical research.5)

Synthetic Organic Chemistry

Cyanine & Squarylium Dyes

Cyanine & Squarylium Dyes

Synthetic Organic Chemistry

D4773

D4456

S N

S

S CH CH CH CH CH CH CH

CH2CH3

I

N

CH2CH3

CH2CH2CH3

Materials Chemistry

CH CH CH CH CH

CH CHCH

CH2CH3

N CH2CH3

CH3 CH3

I

N

CH3 CH3

N (CH CH) CH 3 (CH2)4SO3

CH2CH2CH3

D4463

N

P0156

S

N

P0436

I

I0535

N (CH2)4SO3Na

N Cl

CH CHCH

CH2CH3

CH2CH3

D4464

N

CH3

CH3

CH3

CH3

CH CH CH CH CH

(CH2)4SO3Na

N (CH2)4SO3

N

CH3

CH3

CH3

CH3

CH CH CH

(CH2)4SO3Na

N (CH2)4SO3

Product No.

Product Name

B4342 B4649 C0426 C0436 D4453 D4457 A2684 D4454 D4773 D4456 I0535 P0156 P0436 D4463 D4464

2,4-Bis[4-(diethylamino)-2-hydroxyphenyl]squaraine 2,4-Bis[8-hydroxy-1,1,7,7-tetramethyljulolidin-9-yl]squaraine Cryptocyanine Cyanine 3,3'-Diethyloxacarbocyanine Iodide 3,3'-Diethyloxadicarbocyanine Iodide 1,1'-Diethyl-3,3,3',3'-tetramethylindocarbocyanine Iodide 3,3'-Diethylthiacarbocyanine Iodide 3,3'-Diethylthiatricarbocyanine Iodide 3,3'-Dipropylthiadicarbocyanine Iodide Indocyanine Green Pinacyanol Chloride Pinacyanol Iodide 3,3,3',3'-Tetramethyl-1,1'-bis(4-sulfobutyl)benzoindodicarbocyanine Sodium Salt 3,3,3',3'-Tetramethyl-1,1'-bis(4-sulfobutyl)indocarbocyanine Sodium Salt

Unit Size 1g 1g 200mg 1g 1g 1g 1g 1g 200mg 100mg 100mg 1g 1g 1g

References 1) 2) 3) 4) 5) 6) 7) 8) 9) 10)

292

N

Y. Y. Davidson, B. M. Gunn, S. A. Soper, . 1996, , 211. A. Mishra, R. K. Behera, P. K. Behera, B. K. Mishra, G. B. Behera, . 2000, , 1973. 1995, Review: Z. Zhu, , 77. H. Oba, M. Abe, M. Umehara, T. Sato, Y. Ueda, M. Kunikane, . 1986, , 4023. 2014, X. H. Zhang, Q. Liu, H. J. Shi, L. Y. Wang, Y. L. Fu, X. C. Wei, L. F. Yang, , 232. K.-Y. Law, F. C. Bailey, L. J. Bluett, . 1986, , 1607. 1993, K.-Y. Law, F. C. Bailey, , 1. A. Burke, L. Schmidt-Mende, S. Ito, M. Grätzel, . 2007, 234. T. Maeda, Y. Hamamura, K. Miyanaga, N. Shima, S. Yagi, H. Nakazumi, . 2011, , 5994. B. Zhang, W. Zhao, Y. Cao, X. Wang, Z. Zhang, X. Jiang, S. Xu, . 1997, , 237.

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

5g 5g 1g 5g 5g 200mg 5g 5g 5g 1g 1g 1g 5g 5g 5g

Dipyrromethene Dyes

Dipyrromethene is a unit structure of porphyrin and can coordinate to main group elements and transition metals as a monoanionic bidentate ligand to form complexes. Among them, a dipyrromethenecoordinated boron complex (boron dipyrromethene) shows a very small Stokes shift, high fluorescent quantum efficiency that is independent of solvent polarity, large molar absorption coefficient, and sharp excitation and emission spectra. It is expected that dipyrromethene dyes are alternative fluorescent dyes to fluorescein and rhodamine dyes. Applications of dipyrromethene dyes are fluorescent labeling reagents, laser dyes, and electronic materials. A chemical modification of boron dipyrromethene controls optical properties more easily than other fluorescent dyes.

B4489 CH3

CH3 (CH3)3C

N CH3

F

B

N F

D4341

CH3

CH3

CH3

C(CH3)3 CH3

CH3(CH2)3

N CH3

F

CH3

CH3

CH3

N

CH3

CH3

F

F

CH3

CH3

N

N B

E1065

CH3 NaO3S

(CH2)3CH3

N B

F

D4593 CH3

CH3

N B

F

F

CH3

CH3

CH3CH2

N CH3

Product No.

Product Name

B4400

[[(4-tert-Butyl-3,5-dimethyl-1H-pyrrol-2-yl)(4-tert-butyl-3,5-dimethyl-2H-pyrrol-2-ylidene)methyl]methane](difluoroborane) [[(4-Butyl-3,5-dimethyl-1H-pyrrol-2-yl)(4-butyl-3,5-dimethyl-2H-pyrrol-2-ylidene)methyl]methane](difluoroborane) [[(3,5-Dimethyl-1H-pyrrol-2-yl)(3,5-dimethyl-2H-pyrrol-2-ylidene)methyl]methane](difluoroborane) [[(3,5-Dimethyl-4-sulfo-1H-pyrrol-2-yl)(3,5-dimethyl-4-sulfo-2H-pyrrol-2-ylidene)methyl]methane](difluoroborane) Disodium Salt [[(4-Ethyl-3,5-dimethyl-1H-pyrrol-2-yl)(4-ethyl-3,5-dimethyl-2H-pyrrol-2-ylidene)methyl]methane](difluoroborane)

B4489 D4341 D4593 E1065

CH3

CH3 SO3Na

F

B

N F

Materials Chemistry

B4400

CH3 CH2CH3 CH3

Unit Size

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

Synthetic Organic Chemistry

Dipyrromethene Dyes

200mg 200mg 1g 200mg 200mg

293

Materials Chemistry

Synthetic Organic Chemistry

Xanthene Dyes

Xanthene Dyes Both cationic and anionic xanthene dyes are known to be efficient fluorescent dyes. Functional groups on the xanthene moiety control their fluorescent colors. For instance, there are the cationic dyes of rhodamine B with a dialkylamino group as a red fluorescent dye, fluorescein as a green fluorescent dye, and the anionic dye of eosin (brominated fluorescein) as a red fluorescent dye. Applications of xanthene dyes involve optical materials and organic dyes for medical diagnosis research. Several characteristic features of xanthene dyes are large absorption and luminescence, excellent light resistance, low toxicity in-vivo, and relatively high solubility in water. Since xanthene dyes have a sensitizing effect, their applications for dye sensitized solar cells (DSSC) have been reported.1) We can expect that the xanthene dyes fabricate DSSC devices at low cost, because they are metal-free, although the power conversion efficiency of xanthene dyes are lower than those of ruthenium-based dyes. Further research has been in progress with a combination of several xanthene dyes to increase power conversion efficiency.2) There is an application of xanthene derivatives for a laser dye. A dye laser requires coumarin and rhodamine dyes as an organic medium. They all oscillate in the visible area. Among these xanthene dyes, the rhodamine 6G is mainly used for a laser dye.3) Et Et

Br

Et

N

N

O

Et

HO

O

Br

CO2H

CO2Na

Fluorescein

Eosine

[R0040]

[F0095]

[T0037]

T0037 CH2CH3 N CH2CH3

O

O

Rhodamine B

A0600 CH3CH2

O

Br

Cl CO2H

CH2CH3 N

Br

NaO

O

E0204 Br

NaO

O

O

Br

SO3

T0050 Br

Br

Br

SO3Na

O

NaO

R0041 Br

Br O

O2N

NaO

C ONa

C ONa

O

O

O

Br

NO2

I

Br

Cl

O

NaO

Br

I

I O

I Cl

C ONa

C ONa O

O Cl

Cl

Cl

Cl Cl

Cl

A1906

D0207

D1120 OH

CH3 H N

O

CH3 SO3Na

CH3

HO

CH3

H N

SO3

O

O

Br

D0424 Br

OH

Br

HO

O

D1118 O

NaO

O

HO

O

Cl

Cl

HO

OH

C ONa

O

O CH3

O

T0557

F0095 I

NaO

I O

O

I

I C ONa O

294

HO

F0139 O

OH NaO

O O

F0142 I

I

O I COONa

NaO

. H2O

N

. xH2SO4 . xH2O CH3

F0001 Br

I O

O

OH

Br SO3H

O

Br O

Br Cl Cl Cl

I O

NaO

Br

I

I O

O

I

COONa

Cl

Cl

Cl

COONa Cl Cl

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

Xanthene Dyes

F0143

A0601

CH3CH2

N

O

N

CH2CH3

T0450

HO

CH2CH3

HO

OH O

P0572

HO

O

R0040 OH

O HO

OH

HO

OH O

O CH3CH2

OH

CH2CH3 N

Cl

O

C OH

SO3H

O

O

R0039

S0132 HO

CH3CH2HN

O

T0036 O

OH

NHCH2CH3

CH3

CH3

Cl

T0049 Br

KO

T0066 Br

Br O

Br

O

C OCH2CH3 O

HO

O Br

Br

COOK

SO2

HO

Br O

F0096

HO I

I O

NaO

O

Cl

Br C OH

Cl

Cl

O Cl

Cl

C OH O Cl Cl

F0027 O

O

KO

O

Materials Chemistry

T0124

O

O

Cl

I

CH2CH3 N CH2CH3

O

SO3

SO3Na

Synthetic Organic Chemistry

CH2CH3

O

OH

O

I

C ONa

COOK

O

O

Product No.

Product Name

A0600 T0037 E0204 T0050 R0041 A1906 D0207 D1120 D0424 D1118 T0557 F0095 F0139 F0142 F0001 F0143 A0601 T0450 P0572 R0040 R0039 S0132 T0036 T0049 T0066 T0124 F0096 F0027

Acid Red 52 Acid Red 87 Acid Red 91 Acid Red 92 Acid Red 94 Acid Red 289 Bromopyrogallol Red Dibromofluorescein (contains Mono-, Tri- and Tetra-) 2',7'-Dichlorofluorescein Sodium Salt 9-(4'-Dimethylaminophenyl)-2,6,7-trihydroxyfluorone Sulfate Hydrate Erythrosine B Fluorescein Food Red No. 3 Food Red No. 104 Food Red No. 105 Food Red No. 106 Gallein Phenylfluorone Pyrogallol Red Rhodamine B Rhodamine 6G Sulfonfluorescein Tetrabromofluorescein Potassium Salt 2',4',5',7'-Tetrabromo-3,4,5,6-tetrachlorofluorescein 3,4,5,6-Tetrachlorofluorescein Tetraiodofluorescein Uranine Uranine K

Unit Size

1g 1g

25g

100g

1g

25g 1g

25g

25g 25g 25g 25g 25g 25g 5g 5g 25g 1g 25g 500g 25g 25g 25g 25g 25g 1g 1g 250g 25g 5g 25g 25g 1g 25g 500g 25g

References 1) H. Tsubomura, M. Matsumura, Y. Nomura, T. Amamiya, 2) S. Rani, P. K. Shishodia, R. M. Mehra, 3) J. Loerke, F. Marlow, . 2002, , 1745.

1976, , 402. . 2010, , 043103.

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

295

Materials Chemistry

Synthetic Organic Chemistry

DCM Dyes

DCM Dyes DCM dye consists of a pyranylidene malononitrile as an electron acceptor and a 4-aminostyryl group as an electron donor. Chemical modifications of the substituent on the pyran ring and amino group control the wavelengths of absorption and luminescence. The DCM dyes are useful for laser oscillation and a red dopant for an organic light-emitting diode device. This dye is a low band gap material with good efficiency and long lifetime.

D4700 CH3 CH3

D2849 NC

CN NC

CN

CH3 N

CH CH

O

C CH3 CH3

CH3 CH3

296

CH3 CH3

N

CH CH

O

CH3

Product No.

Product Name

D4700 D2849

DCJTB 4-(Dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran

Unit Size

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

200mg 500mg

Quinacridone Dyes

Quinacridone dyes were originally used as red pigments having clear color and durability. They are useful for painting of automobiles, printing ink and coloring of plastics. In the research field of organic electronics, quinacridone dyes are applied to solar cells and organic light-emitting diodes (OLED). Quinacridones easily show intermolecular stacks in face-to-face mode and form strong intermolecular hydrogen bondings (NH•••O). Thus, these facts indicate that quenching of emission occurs under a concentrated condition. On the other hand, quinacridone dyes are strongly luminescent in solution, and are useful for luminescent dopant materials even if they are used in the solid state. In fact, they are green luminescent dopants for an OLED device. In order to decrease intermolecular hydrogen bonding, we can introduce a group on the nitrogen to avoid intermolecular quenching. Introduction of alkyl groups enhances solubility, because quinacridones usually are poorly soluble. D4697 (CH2)3CH3

O

N

O

(CH2)3CH3

CH3

CH3

CH3

O

(CH2)3CH3

O

N

N N

N O

(CH2)3CH3 CH3

Q0083 Q0057

D3227 D2687

CH3

H N

N O

CH3

O

Materials Chemistry

D4780

O

N H

Product No.

Product Name

D4780 D4697 D3227 D2687 Q0083 Q0057

N,N '-Dibutylquinacridone 5,12-Dibutyl-1,3,8,10-tetramethylquinacridone (This product is only available in Japan.) N,N '-Dimethylquinacridone (purified by sublimation) N,N '-Dimethylquinacridone Quinacridone (purified by sublimation) Quinacridone

Synthetic Organic Chemistry

Quinacridone Dyes

Unit Size 200mg 200mg 1g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

1g 1g 1g 5g 1g 25g

297

Materials Chemistry

Synthetic Organic Chemistry

Metal-Organic Frameworks (MOFs / PCPs) & Related Ligands

Metal-Organic Frameworks (MOFs / PCPs) & Related Ligands Porous metal-organic frameworks (MOFs) (other name: porous coordination polymers (PCPs)) have attracted wide scientific attention for the potential application to gas storage, gas separation, catalysis and nanospace engineering.1) MOFs (PCPs) are constructed mainly by coordination bonds between metal cations and multidentate ligands. Their specificities depend on the pore shape, size, and chemical environments of the voids or channels. Kitagawa . have reported the first utilization of a MOF as an electrocatalyst for oxidation of ethanol to aldehyde, for which the potential was comparable with Pt-based catalysts.2) Recently, Kaneko, Kanoh, Kondo, Kajiro, . have developed a quite unique Cu complex MOF [Cu(bpy)(BF4)2(H2O)2]bpy (bpy = 4,4’ -bipyridine),3) named as -ELM-11 (ELM stands for Elastic LayerStructured MOF). Upon heating and dehydration, -ELM-11 converts to an innovative and stable gas absorbent ELM-11 [Cu(bpy)2(BF4)2] (Figure 1). ELM-11 has structural flexibility, and its structural transformation occurs easier than traditional rigid MOFs. And the gate type adsorption isotherm on ELM-11, which has a predominantly rectangular shaped hysteresis, is quite unique (Figure 2).

Figure 1. Structure Transformation between

-ELM-11 and ELM-11

-ELM-11 is easily converted to ELM-11 by an activation process (dehydration). Recommended conditions are 120℃ for 3 h in vacuo. ELM-11 is stable on drying at rt. ELM-11 rapidly absorbs moisture in atmospheric conditions and changes its structure to -ELM-11, but can be re-transformed.

Figure 2. Schematic representation of the gate adsorption of CO23a) -ELM-11 is also utilized as a catalyst in organic synthesis for molecular oxygen-derived oxidation and epoxide alcoholysis (Scheme).4) 298

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

Metal-Organic Frameworks (MOFs / PCPs) & Related Ligands

OSi(CH3)3

Synthetic Organic Chemistry

4a)

CH3

O2, pre-ELM-11 (10 mol%)

O

OH CH3 4b)

O2, pre-ELM-11 (10 mol%) (0.5 eq.) LiOH - H2O (0.8 eq.) P(OEt)3

CH3

O

Y. 85 %

EtOH - H2O, 0 ºC, 4.5 h

Y. 84 %

EtOH, 80 ºC, 14.5 h

OCH3

O CH3OH

4c)

OH

pre-ELM-11 (9 mol%) rt, 2 h

Y. 94 %

Materials Chemistry

Scheme. Molecular oxygen-derived oxidation and epoxide alcoholysis using

-ELM-11

C2409

MOF/PCP

[Cu(bpy)(BF4)2(H2O)2]bpy

Product No.

Product Name

C2409

pre-ELM-11

Unit Size 5g

A0088

A1358

A1290 O

O HO

Ligands for MOF/PCP

O

OH

C OH

O

. xH2O O

OH

C OH

OH

H2N O

A1291

B4294

B0043

D0864

B1191 O

O C OH

C OH

COOH

CN

NH2

O

O

HO C

NC

C OH

CN

HOOC

COOH

HO C O

O

B3792 O HO C

B4297

B3622

B3502

C OH

O

O O

C OH

N N

O

B1876

O

N

HO C

C OH

HO C C OH

O

HO C

C OH

N N

N

N

N

O

O

HO C

C OH N

N

O

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

299

Metal-Organic Frameworks (MOFs / PCPs) & Related Ligands

Synthetic Organic Chemistry

B3533

B0468

O HO C

B0863

O N

N

C OH

B2496

N

B3984

N

N

N

N

N

B4023

B1321

N CH2

HO C C OH

Materials Chemistry

COOH

D4273

C OH

O

O

C2029

COOH

C OH

N

CH2

N

N

O

HO C

Br

N

N

C2198 O

C OH

N

N

N

C2502 O

N

B0469

D0134

HOOC

O

COOH

D4275

D3899 O C OH

COOH

N H2N

HOOC

N S

NH2

S

HC C

N

C CH N H

N

COOH

OH HO C OH O

D4068

D3752

D0276

D0938

H0794

O

COOH

C OCH3 N

CH2CH2

N

N

CH

CH

N

N

CH2CH2CH2

N

O Br

HO

C OCH3

H1385

I0001

I0003

I0155

O

HO C

N

OH

N H

N

O

O

M0345

N0606 C OH

CH3

O

. H2O

N

N

C OH O

300

N H

N

N

C OH

N

B0039 COOH

O

. H2O

COOH

C OH

OH

O

C OH

P0554

O

HO

COOH

O

P0550

C OH

HOOC

P0544

OH

O

COOH

O

P1048 N

O

N

NO2

C OH

HOOC

HO C

P0287

O

P0545

C OH

OH

C OH

O2N

O

C OH

P0221

C OH

N0770

O

O

O

O

O CH3O

C OH

C OH C OH

O

C OH

N0377

N

N0272

O

C OH O

N0526 O

N0520

O

N H

HO C

C OH

N H

M1835

O

C OH

COOH

HO N

C OH O

OH

N O

O

HOOC COOH

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

Metal-Organic Frameworks (MOFs / PCPs) & Related Ligands

S0850

T0166

T0975

T2760

B0042

C OH

HOOC

HO

OH CH N N CH

HOOC

O

COOH

C OH

COOH

C CH

COOH

HC C

COOH

C CH

COOH

O

T1937

Synthetic Organic Chemistry

O

T2647 N

N

COOH

N N

N

N

HOOC

COOH

Product Name

A0088 A1358 A1290 A1291 B4294 B0043 D0864 B1191 B3792 B4297 B3622 B1876 B3502 B3533 B0468 B0863 B3984 B0469 B2496 B4023 B1321 C2502 C2198 C2029 D4273 D0134 D4275 D3899 D4068 D3752 D0276 D0938 H0794 H1385 I0001 I0003 I0155 M1835 M0345 N0606 N0526 N0377 N0770 N0520 N0272 P0221 P0287 P0544 P0545 P1048

Acetylenedicarboxylic Acid 1,3-Adamantanedicarboxylic Acid 5-Aminoisophthalic Acid Hydrate 2-Aminoterephthalic Acid 1,3,5-Benzenetricarbonitrile 1,3,5-Benzenetricarboxylic Acid 2,2'-Biphenyldicarboxylic Acid 4,4'-Biphenyldicarboxylic Acid Biphenyl-3,3',5,5'-tetracarboxylic Acid 2,2'-Bipyrazine 2,2'-Bipyridine-3,3'-dicarboxylic Acid 2,2'-Bipyridine-4,4'-dicarboxylic Acid 2,2'-Bipyridine-5,5'-dicarboxylic Acid 2,2'-Bipyridine-6,6'-dicarboxylic Acid 2,2'-Bipyridyl 2,4'-Bipyridyl 3,3'-Bipyridyl 4,4'-Bipyridyl 2,2'-Bipyrimidyl 1,4-Bis[(1H-imidazol-1-yl)methyl]benzene Bromoterephthalic Acid 1,2,3,4-Cyclobutanetetracarboxylic Acid 1,2,4,5-Cyclohexanetetracarboxylic Acid 1,3,5-Cyclohexanetricarboxylic Acid (cis- and trans- mixture) 2,2'-Diamino-4,4'-bithiazole 1,4-Diazabicyclo[2.2.2]octane 3,6-Diethynylcarbazole 2,5-Dihydroxyterephthalic Acid Dimethyl 5-Bromoisophthalate 1,2-Di(4-pyridyl)ethane 1,2-Di(4-pyridyl)ethylene 1,3-Di(4-pyridyl)propane 5-Hydroxyisophthalic Acid 2-Hydroxyterephthalic Acid Imidazole 1H-Imidazole-4,5-dicarboxylic Acid Isophthalic Acid 5-Methoxyisophthalic Acid 2-Methylimidazole 1,4-Naphthalenedicarboxylic Acid 2,3-Naphthalenedicarboxylic Acid 2,6-Naphthalenedicarboxylic Acid 1,4,5,8-Naphthalenetetracarboxylic Acid (contains Monoanhydride) 5-Nitroisophthalic Acid Nitroterephthalic Acid 1,10-Phenanthroline Monohydrate Phthalic Acid Pyrazine 2,3-Pyrazinedicarboxylic Acid 3,5-Pyrazoledicarboxylic Acid Monohydrate

Materials Chemistry

Product No.

Unit Size 5g 5g 25g

25g

1g 100g 25g 5g

1g 100mg

25g

1g 100g 1g 1g 25g 200mg 5g

5g 5g 200mg 25g 100g 200mg 5g 1g 1g 10g 25g 25g 1g 25g 100g 5g 25g 25g

100g 5g 25g 25g 25g 1g 25g 25g 5g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

25g 25g 500g 25g 5g 500g 100g 25g 200mg 100mg 5g 1g 1g 5g 500g 5g 5g 100g 1g 5g 25g 1g 25g 25g 1g 500g 1g 25g 5g 5g 25g 500g 500g 5g 500g 25g 500g 5g 500g 25g 25g 100g 250g 500g 25g 25g 500g 500g 25g 25g

301

Synthetic Organic Chemistry

Metal-Organic Frameworks (MOFs / PCPs) & Related Ligands

Product No.

Product Name

P0550 P0554 B0039 S0850 T0166 T0975 T2760 B0042 T1937 T2647

2,3-Pyridinedicarboxylic Acid 2,6-Pyridinedicarboxylic Acid Pyromellitic Acid Salicylaldehyde Azine Terephthalic Acid Tetrahydrofuran-2,3,4,5-tetracarboxylic Acid 1,3,5-Triethynylbenzene Trimellitic Acid 2,4,6-Tri(4-pyridyl)-1,3,5-triazine (purified by sublimation) 1,3,5-Tris(4-carboxyphenyl)benzene

Unit Size

25g

25g 25g 25g 5g 25g 25g 1g 100g 1g 1g

500g 500g 500g 25g 500g 500g 5g 500g 5g 5g

References

Materials Chemistry

1) Reviews of metal-organic frameworks (MOFs / PCPs) a)“Chemistry of Coordination Space”, ed. by H. Nishihara, . 2007, , 2489-2766. b) M. P. Suh, Y. E. Cheon, E. Y. Lee, . 2008, , 1007. c) A. Corma, H. García, F. X. L. Xamena, . 2010, , 4606. 2) Electrocatalyst for ethanol oxidation L. Yang, S. Kinoshita, T. Yamada, S. Kanda, H. Kitagawa, M. Tokunaga, T. Ishimoto, T. Ogura, R. Nagumo, A. Miyamoto, M. Koyama, . 2010, , 5348. 3) For gas storage and gas separation research of pre-ELM-11 a) D. Li, K. Kaneko, . 2001, , 50. b) A. Kondo, H. Noguchi, S. Ohnishi, H. Kajiro, A. Tohdoh, Y. Hattori, W.-C. Xu, H. Tanaka, H. Kanoh, K. Kaneko, . 2006, , 2581. 2007, c) H. Noguchi, A. Kondo, Y. Hattori, H. Kajiro, H. Kanoh, K. Kaneko, , 248. d) H. Kanoh, A. Kondo, H. Noguchi, H. Kajiro, A. Tohdoh, Y. Hattori, W.-C. Xu, M. Inoue, T. Sugiura, K. Morita, H. Tanaka, T. Ohba, K. Kaneko, . 2009, , 1. e) H. Kajiro, A. Kondo, K. Kaneko, H. Kanoh, . 2010, , 3803. f) Nippon Steel Corporation, Nippon Steel Chemical Co., Ltd., Institute of Research and Innovation, Jpn. Kokai Tokkyo Koho 2005 162624; Nippon Steel Corporation, Nippon Steel Chemical Co., Ltd., Institute of Research and Innovation, Jpn. Kokai Tokkyo Koho 2005 162625; Nippon Steel Corporation, Institute of Research and Innovation, Jpn. Kokai Tokkyo Koho 2005 336129; Nippon Steel Corporation, Jpn. Kokai Tokkyo Koho 2005 232031. 4) For catalysis research of pre-ELM-11 a) T. Arai, H. Takasugi, T. Sato, H. Noguchi, H. Kanoh, K. Kaneko, A. Yanagisawa, . 2005, , 1590. b) T. Arai, T. Sato, H. Noguchi, H. Kanoh, K. Kaneko, A. Yanagisawa, . 2006, , 1094. c) D. Jiang, T. Mallat, F. Krumeich, A. Baiker, . 2008, , 390.

302

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

Organic-Inorganic Perovskite Precursors

Inorganic Layer (2D Perovskite)

Inter-Layer Distance

Organic Layer

An application of organic-inorganic perovskite is a perovskite solar cell.11) This solar cell can be usually fabricated by the three-dimensional cubic perovskite [(MeNH3)MX3]. Research on the perovskite solar cell recently received much attention. Power conversion efficiency of this solar cell is more than those of organic photovoltaics (OPV) and dye-sensitized solar cells (DSSC), and the device can be fabricated by solution-process at low cost.

A2778

B4566 NH2

. HI

B4434 CH2NH2

. HI

B4433 CH3

CH3

C NH2 CH3

. HI

CH3(CH2)3NH2 . HI

D4667

CH3

N H

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

CH3

. HBr

303

Materials Chemistry

‘Perovskite’originates from the mineral name of calcium titanate (CaTiO3) and the compounds with formula of ABO3 generally belong to a perovskite-type compound, where the A is a divalent and B is a tetravalent metal ion. A perovskite with cubic or orthorhombic phases shows ferroelectricity, for instance, barium titanate (BaTiO3) is a ferroelectric or piezoelectric material.1) High temperature superconductive oxides with unit of a copper oxide are obtained from all perovskite compounds.2) These perovskite compounds consist of metal ions and oxygen atoms, and are manufactured by a physical procedure (eg. sintering method).3) Modification of the metal ion and a changing ratio of the metal ion components can drastically control physical properties of the perovskite. In addition to the oxide perovskites, halide-based perovskites are also well known. On the other hand, one can replace the cationic component with an organic ammonium. In this case, a chemical method can provide a perovskite compound. This perovskite compound is called an‘organicinorganic perovskite compound’ , because it contains an organic component. A metal ion component usually involves tin or lead.4,5) This perovskite compound has the general formula [(RNH3) MX ], in which modifications of metal (M), halide (X) and organic groups (R) precisely control physical properties. Among them, the tin perovskite is relatively better for electrical conduction,6) and the lead one is better for optical properties.7) A chemical modification of the halide controls band gap.8) Selection of organic ammonium halide, metal halide and their mixing ratio changes the component ratio of the halide. The organic groups are selected from methyl, long alkyls, phenyl, benzyl, phenethyl and so on. Diversity of these organic groups allows controlling the structure of a perovskite compound. For instance, a perovskite compound with R = methyl provides [(MeNH3)MX3] having a three-dimensional cubic perovskite structure.9) A perovskite compound with R = C H2 +1 ( ≥ 2) provides a two-dimensional perovskite layer and the length of alkyl group can control the inter-layer distance.10)

Synthetic Organic Chemistry

Organic-Inorganic Perovskite Precursors

Organic-Inorganic Perovskite Precursors

Synthetic Organic Chemistry

D4643

D4555

N H

CH3

. HI

G0449

CH3

H N

CH3

. HI

G0450

NH H2N

Materials Chemistry

CH3

E1045

H2N

P2213

CH3CH2NH2

. HI

I0935

NH

. HBr NH2

F0973

. HI NH2

F0974

NH H

H

I0934

CH3

NH2 CH3

. HI

NH

. HBr

NH2

. HI

NH2

M2556

CH3 CH3

NH2

. HI

CH3NH2

. HI

P2212 CH2CH2NH2

. HI CH3

NH2 . HI

Product No.

Product Name

A2778 B4566 B4434 B4433 D4667 D4643 D4555 E1045 F0973 F0974 G0449 G0450 I0935 I0934 M2556 P2213 P2212

Aniline Hydroiodide Benzylamine Hydroiodide tert-Butylamine Hydroiodide Butylamine Hydroiodide Diethylamine Hydrobromide Diethylamine Hydroiodide Dimethylamine Hydroiodide Ethylamine Hydroiodide Formamidine Hydrobromide Formamidine Hydroiodide Guanidine Hydrobromide Guanidine Hydroiodide Isobutylamine Hydroiodide Isopropylamine Hydroiodide Methylamine Hydroiodide 2-Phenylethylamine Hydroiodide Propylamine Hydroiodide

Unit Size

1g

1g 1g 1g 1g 1g 1g 1g 1g 1g 1g 1g 1g 1g 1g 5g 1g 1g

5g 5g 5g 5g 5g 5g 5g 5g 5g 5g 5g 5g 5g 5g 25g 5g 5g

References 1) 2) 3) 4) 5) 6) 7) 8) 9) 10) 11)

304

E. Sawaguchi, Y. Akishige, M. Kobayashi, . 1985, , 480. 1989, Y. Tokura, H. Takagi, S. Uchida, , 345. F. S. Galasso, M. Kestigan, . 1973, , 142. 1994, D. B. Mitzi, C. A. Feild, W. T. A. Harrison, A. M. Guloy, , 467. K. Liang, D. B. Mitzi, M. T. Prikas, . 1998, , 403. Y. Takahashi, R. Obara, Z.-Z. Lin, Y. Takahashi, T. Naito, T. Inabe, S. Ishibashi, K. Terakura, 5563. N. Pellet, P. Gao, G. Gregori, T.-Y. Yang, M. K. Nazeeruddin, J. Maier, M. Grätzel, S. A. Kulkarni, T. Baikie, P. P. Boix, N. Yantara, N. Mathews, S. Mhaisalkar, Y. Kawamura, H. Mashiyama, K. Hasebe, . 2002, , 1694. 1990, T. Ishihara, J. Takahashi, T. Goto, , 11099. A. Kojima, K. Teshima, Y. Shirai, T. Miyasaka, . 2009, , 6050.

. 2011, . 2014, 2014, , 9221.

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

, , 3151.

Silane Coupling Agents

Silane coupling agents are organosilicon compounds having two functional groups with different reactivity. One of the two functional groups reacts with organic materials and the other reacts with inorganic materials. Their general structure is as follows:

Y R Si

X

3

A1275

A1538

A0785

CH3

Olefinyl Silanes

A1504

CH2

OCH3

C1208

CH2

OCH3

CH3 CH2

CH2 CH

CH3

Si

CH Si Cl

Cl

CH2 CH Si OCH2CH3 OCH2CH3

Product No.

Product Name

A1275 A1538 A0785 A1504 B3214 C1208

Allylchlorodimethylsilane Allyltrichlorosilane Allyltriethoxysilane Allyltrimethoxysilane [Bicyclo[2.2.1]hept-5-en-2-yl]triethoxysilane (mixture of isomers) Chlorodimethylvinylsilane

CH2 CHCH2

Si OCH2CH3 OCH2CH3

D3386 OCH3

OCH2CH3 CH2

CH

Si CH3

CH2 CH

Si

CH3

OCH3

OCH2CH3

V0042 OCH2CH3

Cl

Cl

D2318

V0044 Cl

CH Si OCH2CH3

Si Cl

CH3

T0407

OCH2CH3

Cl CH2 CHCH2

CH3

Si(OCH2CH3)3

Si OCH3

V0046

Si Cl CH3

B3214

CH2 CHCH2

CHCH2

V0048 OCH3

CH2 CH Si

OCH3

OCH3

OCH2CH2OCH3 CH2 CH Si OCH2CH2OCH3 OCH2CH2OCH3

Unit Size 10mL 5g

25mL 25g 10mL 5mL 25mL 1g 5g 25mL 100mL

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

305

Materials Chemistry

Where Y denotes a functional group that links with organic materials, e.g. vinyl, epoxy, amino group and so on. X is a functional group that undergoes hydrolysis by water or moisture to form silanol. This silanol links with inorganic materials. Representative examples of X include chlorine, alkoxy, and acetoxy group. Silane coupling agents are effective for the improved adhesion at the interface between the organic and inorganic materials and have been frequently utilized to enhance the strength and improve the performance of glass-fiber reinforced plastics. Recently, they have been used in the manufacture of inorganic-organic hybrid materials such as the laminating board for printed circuit boards, artificial marble, plastic magnets, and silica-immobilized bioactive compounds. In addition to the original purpose of improving the adhesiveness of an interface, different applications are being explored. Examples include synthesis of moisture crosslinkable polymers using the reactivity of hydrolytic functional group, to give antistatic and antibacterial properties from surface treatment using silane coupling agents. It is expected that silane coupling agents will be applied in many fields.

Synthetic Organic Chemistry

Silane Coupling Agents

Materials Chemistry

Synthetic Organic Chemistry

Silane Coupling Agents

Product No.

Product Name

D2318 D3386 V0046 T0407 V0044 V0042 V0048

Diethoxymethylvinylsilane Dimethoxymethylvinylsilane Dimethylethoxyvinylsilane Trichlorovinylsilane Triethoxyvinylsilane Vinyltrimethoxysilane Vinyltris(2-methoxyethoxy)silane

Unit Size 25g 25g 100g 25mL 100mL 25mL 100mL 25mL

D4679

M1530

O

Acryloyloxyalkyl Silanes

T2676

CH2

CH3

A1597

O

OCH2CH3

CH2

CH C O(CH2)3

OCH2CH3

CH3

CH3

Si OCH3

CH3

OCH3

CH2 C C O(CH2)3 Si CH3

OCH3

OCH3

C C O(CH2)3 Si

CH3

O CH2

CH3

CH C O(CH2)3 Si OCH3 CH3

OCH3

M1324

O

OCH3

O CH2

OCH2CH3

M0725

O

OCH2CH3

CH2 C C O(CH2)3 Si

M2525

OCH2CH3

C C O(CH2)3 Si

OCH3

O CH2

CH3

OCH3

OSi(CH3)3

C C O(CH2)3 Si OSi(CH3)3

Product No.

Product Name

D4679 M1530 M2525 T2676 A1597 M0725 M1324

3-[Diethoxy(methyl)silyl]propyl Methacrylate 3-[Dimethoxy(methyl)silyl]propyl Methacrylate 3-(Methoxydimethylsilyl)propyl Acrylate (stabilized with MEHQ) 3-(Triethoxysilyl)propyl Methacrylate (stabilized with HQ) 3-(Trimethoxysilyl)propyl Acrylate (stabilized with BHT) 3-(Trimethoxysilyl)propyl Methacrylate (stabilized with BHT) 3-[Tris(trimethylsilyloxy)silyl]propyl Methacrylate (stabilized with MEHQ)

OSi(CH3)3

Unit Size

D2632 OCH2CH3

O

25mL 25mL 5g 25g 25g 25mL 100mL 500mL 25mL 100mL

G0261

CH2O(CH2)3 Si

Glycidyloxyalkyl Silanes

OCH3

CH3

OCH2CH3

G0210

CH2O(CH2)3 O

OCH3

Si CH3 OCH3

CH2O(CH2)3 O

T2675

OCH2CH3 CH2O(CH2)3 Si O

306

25mL 250g 25mL 500g 500mL 500mL 500mL

OCH2CH3

OCH2CH3

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

Si

OCH3

OCH3

Silane Coupling Agents

Product Name

D2632 G0261 G0210 T2675

Diethoxy(3-glycidyloxypropyl)methylsilane 3-Glycidyloxypropyl(dimethoxy)methylsilane 3-Glycidyloxypropyltrimethoxysilane Triethoxy(3-glycidyloxypropyl)silane

Unit Size 25g

A0876

A1923

CH3

H2N(CH2)3 Si CH3

CH3 CH3

T2868

NH(CH2)3

Product Name 3-(2-Aminoethylamino)propyldimethoxymethylsilane 3-(2-Aminoethylamino)propyltriethoxysilane 3-(2-Aminoethylamino)propyltrimethoxysilane 3-Aminopropyldiethoxymethylsilane 3-Aminopropyldimethoxymethylsilane 3-Aminopropyltriethoxysilane 3-Aminopropyltrimethoxysilane Bis[3-(trimethoxysilyl)propyl]amine [3-(N,N-Dimethylamino)propyl]trimethoxysilane Trimethoxy[3-(methylamino)propyl]silane Trimethoxy[3-(phenylamino)propyl]silane Trimethyl[3-(triethoxysilyl)propyl]ammonium Chloride Trimethyl[3-(trimethoxysilyl)propyl]ammonium Chloride (ca. 50% in Methanol)

CH3CH2O Si

OCH2CH3

CH2CH2 Si OCH2CH3

OCH2CH3

B0393

CH3 CH3

CH3

OCH2CH3

C1468

Cl

CH3(CH2)9

B2010

Si Cl

OCH3

CH3

CH3 CH3

CH3

OCH3

CH2CH2 Si

OCH3

CH3(CH2)3 Si Cl

OCH3

D2262 CH3

Cl CH3(CH2)3 Si Cl

25g 25mL

OCH3 CH3O Si

25mL 500mL 25g 100g 500g 100mL 500mL 25mL 100g 500g 100mL 500mL 25g 500g 5mL 25mL 25g 100g 25g 250g 5g 25g 10g 25g

25g 25mL

B2927

OCH2CH3

Alkyl Silanes

Si Cl

(CH3O)3Si(CH2)3 N CH3 Cl

Unit Size

B4123

CH3 CH3

Cl

CH3

A0876 A1923 A0774 D1980 A2628 A0439 T1255 B2548 D4328 T2868 P1458 T2246 T2796

CH3 C

CH3

CH3 (CH3CH2O)3Si(CH2)3 N CH3

Product No.

B0995

OCH3

OCH3

T2796

OCH3

OCH3

OCH3

Si OCH3

CH3O Si (CH2)3NH(CH2)3 Si OCH3

OCH3

OCH3

CH3NH(CH2)3 Si OCH3

OCH3

OCH3

T2246

OCH3

OCH3 N(CH2)3 Si OCH3

OCH3 H2NCH2CH2CH2 Si OCH3

OCH2CH3

P1458

OCH3

B2548

OCH2CH3 H2N(CH2)3 Si OCH2CH3

OCH3

OCH2CH3

D4328

T1255

OCH3

OCH2CH3 H2N(CH2)3 Si

A0439

H2NCH2CH2NH(CH2)3 Si OCH3

OCH2CH3

OCH3

A2628

OCH3

OCH2CH3

CH3 H2NCH2CH2NH(CH2)3 Si OCH2CH3

CH3

D1590 CH2CH3 CH Si

Cl

CH3 CH3CH2CH2 Si Cl

CH2CH3

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

CH3

307

Materials Chemistry

D1980

H2NCH2CH2NH(CH2)3 Si

25mL 500g 500g 25g

A0774

OCH3

Aminoalkyl Silanes

25g 100g

Synthetic Organic Chemistry

Product No.

Silane Coupling Agents

Synthetic Organic Chemistry

T2116

C1469

CH C

CH3

Si

Cl

CH3(CH2)11 Si Cl

C2280

D1486 OCH3

Materials Chemistry

D1509 CH3

CH3(CH2)11 Si Cl

CH3

H1376

OCH3

O0165

O0256

M0450

O0079

Si Cl

CH3(CH2)17 Si Cl

Cl

O0171 OCH2CH3

OCH2CH3 CH3

Si OCH2CH3

CH3(CH2)7 Si OCH2CH3 OCH2CH3

OCH2CH3

T2875

Cl

CH3

Si

C CH

Cl

CH3

CH3 CH3

Cl CH3(CH2)5 Si Cl Cl

E0189 OCH2CH3

Cl CH3(CH2)13 Si Cl

CH3CH2

Si OCH2CH3 OCH2CH3

Cl

T1078

M0660 iPr

OCH2CH3 OCH2CH3

OCH3 OCH3

Cl

Cl

H0547

Cl

CH3CH2CH2 Si OCH2CH3

Cl

CH3 CH CH2 Si

iPr

Si iPr

OCH3 Cl

CH3 Si OCH3 OCH3

T1801 OCH3

CH3(CH2)7 Si OCH3

308

CH3

OCH3

OCH3

Cl

Cl

Cl

OCH3 CH3(CH2)5 Si

Cl

T2867

CH3CH2 Si

I0452

T0924

CH3(CH2)2 Si Cl

Cl

OCH3

OCH3

Cl

Cl

M0451

OCH3 CH3(CH2)11 Si

Cl

P0371

Si Cl CH3

T2517

CH3(CH2)7 Si Cl

Cl

Cl

OCH2CH3

CH3(CH2)17

E0188

OCH2CH3

OCH3

OCH2CH3

CH3

OCH2CH3

O0168

CH3(CH2)17 Si OCH3

CH3

CH3

Si Cl

H0879

CH3(CH2)5 Si

OCH3

OCH2CH3 CH3(CH2)17 Si OCH2CH3

CH3

OCH2CH3

OCH3

OCH3

CH3

D3383

H1158

CH3(CH2)15 Si OCH3

D1560

OCH2CH3

OCH3

OCH3

Si CH2CH3

CH3(CH2)11 Si OCH2CH3

Cl

E0789

D1594

D1510 Cl

CH3(CH2)7 Si Cl

Si Cl CH3

CH3

Cl

D1827

CH3

Cl

CH3 Cl

SiCl3

CH3

CH2CH3

D0135

CH3(CH2)9 Si Cl

OCH3

CH3

CH3CH2 Si

Cl

Si OCH3

C0892

CH2CH3

CH3

CH3 CH3

CH3CH2 Si

C0306

CH3

CH3 CH3

CH3

T0589

CH3(CH2)2 Si OCH3 OCH3

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

Silane Coupling Agents

1,2-Bis(triethoxysilyl)ethane 1,2-Bis(trimethoxysilyl)ethane Butylchlorodimethylsilane tert-Butyldimethylchlorosilane Butyltrichlorosilane Chloro(decyl)dimethylsilane Chlorodiethylisopropylsilane Chlorodimethylpropylsilane Chloro(dimethyl)thexylsilane Chloro(dodecyl)dimethylsilane Chlorotriethylsilane Chlorotrimethylsilane Cyclohexyltrichlorosilane Cyclohexyltrimethoxysilane Decyltrichlorosilane Dimethylethylchlorosilane Dimethylisopropylchlorosilane Dimethyloctadecylchlorosilane Dimethyl-n-octylchlorosilane Dodecyltrichlorosilane Dodecyltriethoxysilane Dodecyltrimethoxysilane Ethyltrichlorosilane Ethyltrimethoxysilane Hexadecyltrimethoxysilane Hexyltriethoxysilane Hexyltrimethoxysilane Isobutyltrichlorosilane Octadecyltriethoxysilane Octadecyltrimethoxysilane n-Octyltrichlorosilane Thexyltrichlorosilane Trichlorohexylsilane Trichloro(methyl)silane Trichlorooctadecylsilane Trichloro(propyl)silane Trichlorotetradecylsilane Triethoxyethylsilane Triethoxymethylsilane Triethoxy-n-octylsilane Triethoxy(propyl)silane Triisopropylsilyl Chloride Trimethoxy(methyl)silane Trimethoxy-n-octylsilane Trimethoxy(propyl)silane

Unit Size 5g 5g

1g 5mL 5g 5g 25g 25mL 100mL 5g 5g 5g 5mL 25mL

25g 25g

25mL 25mL 25g

25g 5g 25g

5mL

B3282 CH3

Aryl Silanes, Arylalkyl Silanes

D3760

100g

25mL 25mL 25g 25mL 25mL 25mL

B2334

D1147

25g

CH2

CH3 CH2CH2CH2 Si Cl

CH2 Si OCH2CH3

CH3

D2319

C1488 OCH2CH3

Si Cl

5mL 25g 25mL 100g 25g 25mL 5g 25mL 25g 25mL 100g 500mL 25g 25g 25mL 25g 25mL 25mL 100mL 25mL 10mL 250g 500g 25g 25g 500mL 500mL 500g 25g 25mL 250g 25g 25mL 500g 25g 25g 10mL 25mL 500mL 500mL 100g 250mL 500mL 25mL 500mL

Materials Chemistry

Product Name

B4123 B2927 B2010 B0995 B0393 C1468 D2262 D1590 T2116 C1469 T0589 C0306 C0892 C2280 D1486 D0135 D1594 D1560 D1827 D1509 D1510 D3383 E0188 E0789 H1376 H1158 H0879 I0452 O0165 O0256 O0168 T2517 H0547 M0450 O0079 P0371 T0924 E0189 M0451 O0171 T2867 T1078 M0660 T2875 T1801

Synthetic Organic Chemistry

Product No.

CH3

OCH2CH3

P0240

T2852 Cl

CH3

OCH2CH3

OCH3

Si Cl

Si

Si CH3

CH3

OCH2CH3

CH3

SiCl3

CH2CH2 Si Cl

OCH3

Cl CH3 Cl CH Si Cl Cl

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

309

Silane Coupling Agents

Synthetic Organic Chemistry

T2854

T2853

P0735

Cl (CH2)6

OCH3 Si

OCH3

OCH3 CH2

CH

Si

OCH3

OCH3

OCH3

Materials Chemistry

OCH3

OCH3

T3185

CH3

Product No.

Product Name

B2334 B3282 C1488 D1147 D3760 D2319 P0240 T2852 T2854 T2853 P0735 T2869 P0857 T2560 T3185

Benzylchlorodimethylsilane Benzyltriethoxysilane Chlorodimethyl(3-phenylpropyl)silane Chlorodimethylphenylsilane Diethoxy(methyl)phenylsilane Dimethoxymethylphenylsilane Phenyltrichlorosilane Trichloro(phenylethyl)silane (mixture of isomers) Trichloro(6-phenylhexyl)silane Trichloro(3-phenylpropyl)silane Triethoxyphenylsilane Trimethoxy(2-phenylethyl)silane [contains ca. 25% Trimethoxy(1-phenylethyl)silane] Trimethoxyphenylsilane Trimethoxy(p-tolyl)silane Trimethoxy(4-vinylphenyl)silane

Unit Size

C2700 F

Fluoroalkyl Silanes, Fluoroaryl Silanes

T2705

F

CF3(CF2)7CH2CH2 Si Cl Cl

T1770

CH2CH2CH2 Si Cl

T2917

OCH2CH3 CF3(CF2)5CH2CH2 Si OCH2CH3 OCH2CH3

T2918 OCH3

CF3(CF2)7CH2CH2 Si OCH3 OCH3

F

F

CH3

T2876

OCH3

CH3 F

Si F

F

F

OCH2CH3 CF3(CF2)3CH2CH2

Si OCH2CH3 OCH2CH3

T2720 F

OCH3

OCH3 F

O(CH2)11 Si OCH3 F

OCH2CH3

CH3

OCH2CH3

T3158

CF3(CF2)3CH2CH2 Si OCH3

F

OCH2CH3 CF3(CF2)7CH2CH2 Si OCH2CH3

OCH3

5g 25g 25mL 25mL 25g 100mL 500g 25g 25g 25g 500mL 100g 500mL 5g 25g

T2860

Cl

F

5g

Si Cl F

CF3(CF2)5CH2CH2 Si Cl

Cl F

F

Cl

Cl F

5g 5g 25mL 25g 25mL 100mL

F

CH3

T2577 F

25mL 25g

CH3

CH2CH2CH2 Si Cl F

5g 5mL

P1242 F

F

F F

1g

P0854

CH3

T3030 Cl

310

Si

OCH3

OCH2CH3

Cl

OCH3

OCH3 CH2CH2 Si OCH3

Si OCH2CH3

CH2CH2CH2 Si Cl

Cl

P0857

OCH2CH3

Cl

Si Cl

T2560

T2869

F

CF3CH2CH2 Si OCH3

OCH3

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

OCH3

Silane Coupling Agents

Product Name

C2700 P0854 P1242 T2705 T3030 T2577 T2876 T2860 T1770 T2917 T2918 T3158 T2720

Chlorodimethyl[3-(2,3,4,5,6-pentafluorophenyl)propyl]silane Pentafluorophenyldimethylchlorosilane Pentafluorophenylethoxydimethylsilane Trichloro(1H,1H,2H,2H-heptadecafluorodecyl)silane Trichloro[3-(pentafluorophenyl)propyl]silane Trichloro(1H,1H,2H,2H-tridecafluoro-n-octyl)silane Triethoxy-1H,1H,2H,2H-heptadecafluorodecylsilane Triethoxy(1H,1H,2H,2H-nonafluorohexyl)silane Triethoxy-1H,1H,2H,2H-tridecafluoro-n-octylsilane Trimethoxy(1H,1H,2H,2H-heptadecafluorodecyl)silane Trimethoxy(1H,1H,2H,2H-nonafluorohexyl)silane Trimethoxy(11-pentafluorophenoxyundecyl)silane (This product is only available in Japan.) Trimethoxy(3,3,3-trifluoropropyl)silane

Unit Size

B0847

C1402

OCH2CH3

C1259

E0327

OCH2CH3 NCCH2CH2 Si

CH3

OCH2CH3

NC CH2CH2CH2

OCH2CH3

Si Cl

P2258

O

OCH2CH3

HC C CH2O C NH(CH2)3 Si OCH2CH3 OCH2CH3

OCH3

T1915

O H2N C NH(CH2)3

OCH3 CH2CH2

Si OCH3

M1505 OCH2CH3

OCH3 CH3

Si

OCH2CH3

OCH2CH3

OCH2CH3

OCH2CH3

Si (CH2)3SH

HS(CH2)3 Si OCH2CH3 OCH2CH3

OCH3

U0048 OCH2CH3

OCN(CH2)3

Cl(CH2)3 Si

Cl

OCH3

I0556

OCH3 HS(CH2)3 Si OCH3

OCH2CH3

Cl(CH2)3 Si Cl

M1323

O

CH3

M0928

T1253

OCH3

C1207

Si Cl CH3

Cl

Cl(CH2)3 Si CH3

OCH3

OCH2CH3

ClCH2

CH3

OCH3

ClCH2 Si OCH3

CH3

C0844

OCH3

OCH2CH3 ClCH2 Si

5g

BrCH2 Si Cl

OCH3

C1168

5g 5g 5g 5g

CH3

N3(CH2)11 Si OCH3

C3073

5g 1g

C0605

OCH3

Other Silane Coupling Agents

25g 5mL 1g 25g 5g 5g 5g 25g 25g 25g 25g 100mg 25g

Materials Chemistry

A2783

5g 1mL

Synthetic Organic Chemistry

Product No.

O H2N C NH(CH2)3

C0840 OCH3

OCH2CH3 Si

OCH2CH3

ClCH2CH2CH2 Si OCH3

OCH2CH3

OCH3

V0050

OCH3 Si

CH

CH2

OCH3

OCH3

H N

. HCl N H

Si(OCH3)3

Product No.

Product Name

A2783 B0847 C0605 C1402 C3073 C1168

(11-Azidoundecyl)trimethoxysilane (Bromomethyl)chlorodimethylsilane Chloro(chloromethyl)dimethylsilane (Chloromethyl)triethoxysilane (Chloromethyl)trimethoxysilane 3-Chloropropyldimethoxymethylsilane

Unit Size 100mg 25g 25g 250g 10g 5g 25g 5g 25g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

311

Synthetic Organic Chemistry

Silane Coupling Agents

Product No.

Product Name

C0844 T1253 C1259 C1207 E0327 M1323 M1505 M0928 P2258 I0556 U0048 C0840 T1915 V0050

3-Chloropropyltrichlorosilane 3-Chloropropyltriethoxysilane 25mL 2-Cyanoethyltriethoxysilane 25mL (3-Cyanopropyl)dimethylchlorosilane 5mL 2-(3,4-Epoxycyclohexyl)ethyltrimethoxysilane 25mL 3-Mercaptopropyl(dimethoxy)methylsilane (3-Mercaptopropyl)triethoxysilane 25g 100g (3-Mercaptopropyl)trimethoxysilane 25mL 100mL 2-Propynyl [3-(Triethoxysilyl)propyl]carbamate 1g 3-(Triethoxysilyl)propyl Isocyanate 25g 25mL 1-[3-(Triethoxysilyl)propyl]urea (40-52% in Methanol) 3-Trimethoxysilylpropyl Chloride 25mL 1-[3-(Trimethoxysilyl)propyl]urea 25g N-[2-(N-Vinylbenzylamino)ethyl]-3-aminopropyltrimethoxysilane Hydrochloride (30-40% in Methanol)

Unit Size

Materials Chemistry

References 1) E. P. Plueddemann, in 2) K. L. Mittal, in

312

, 2nd ed., Springer US, New York, 1991. , CRC Press, New York, 2009, Vol. 5.

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

25g 500mL 250mL 25mL 500mL 25mL 500g 500mL 5g 100g 500mL 500mL 250g 25mL

Self-Assembled Monolayer (SAM) Forming Agents

Self-assembly is the spontaneous gathering and regular arrangement of atoms, molecules and particles and is observed in various natural environments. There are many reports describing basic and applied research into artificial self-assembly, in particular "self-assembled monolayers (SAMs)" formed by the aggregation of organic molecules on a solid surface. A family of organic silicon compounds, silane coupling agents, can form SAMs on glass, alumina and other inorganic oxide surfaces. Thiols (R-SH) are used to forms SAMs on the surface of metal nanoparticles and metal substrates because of their high affinity for gold, silver and other transition metals. Phosphonic acids (R-PO3H2) combine with the surfaces of many inorganic oxides to form stable SAMs.

. 2005,

J. C. Love, L. A. Estroff, J. K. Kriebel, R. G. Nuzzo, G. M. Whitesides,

Materials Chemistry

Reference , 1103.

Silane Coupling Agents (see p.305)

A0623

B0041

B2888

NH2

SH

SH CH3

Thiols

CH3 SH

SH

B0685

B0686

CH3

C0810

SH

D4286

D0970

E0672

O CH3

CH3

CH3

M1038

HS

CH3

M0404

M1294

H0103

CH3

I0149

CH3

CH3(CH2)15SH

SH

CH3

O

CH2CH3

H0068

CH3 O

HS

SH

CH3

H0029

O

M1067 SH

SH

CH3

SH

CH3

SH

SH

N

D0016

SH

CH3

CH3

SH

D4047

C0727

CH3

M2266

SH

M2433

CH3

SH

M0061

O C OH

CH3

SH

CH3 HS

CH3

OH

HS C CH2CH2OH CH3

Synthetic Organic Chemistry

Self-Assembled Monolayer (SAM) Forming Agents

O HS

OH

SH

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

313

Self-Assembled Monolayer (SAM) Forming Agents

Synthetic Organic Chemistry

M1323

M0928

M1802

M0682

M1041 CH2SH

OCH3

OCH3 CH3

HS(CH2)3 Si OCH3

Si (CH2)3SH

OCH3

OCH3

O HS

OCH3 O

CH3

SH CH3

CH3

CH3

O0005

O0026

O0025

P0836

P0861 SH

CH3

CH3

CH3 C CH2 C SH

CH3(CH2)17SH

CH3

F CH3

F

CH3(CH2)14SH

SH

CH3

F

F

Materials Chemistry

F

P0053

P1715

P0488

T0082

T2972 SH

CH2CH2SH CH3

CH3

SH

SH

CH3(CH2)13SH CF3

U0066

CH3

314

SH

Product No.

Product Name

A0623 B0041 B2888 B0685 B0686 C0727 C0810 D0016 D4047 D4286 D0970 E0672 M1067 M1038 H0029 H0068 H0103 I0149 M0404 M1294 M2266 M2433 M0061 M1323 M0928 M1802 M0682 M1041 O0005 O0026 O0025 P0836

4-Aminobenzenethiol Benzenethiol 2,3-Butanedithiol 1-Butanethiol sec-Butyl Mercaptan Cyclohexanethiol Cyclopentanethiol 1-Decanethiol 4-(Dimethylamino)benzenethiol 3,5-Dimethylbenzenethiol 1-Dodecanethiol 4-Ethylbenzenethiol 2-Ethylhexyl 3-Mercaptopropionate Ethyl 3-Mercaptopropionate 1-Heptanethiol 1-Hexadecanethiol Hexyl Mercaptan Isoamyl Mercaptan Isobutyl Mercaptan 4-Mercaptobenzoic Acid 6-Mercapto-1-hexanol 3-Mercapto-3-methyl-1-butanol 3-Mercaptopropionic Acid 3-Mercaptopropyl(dimethoxy)methylsilane (3-Mercaptopropyl)trimethoxysilane 3-Methoxybutyl 3-Mercaptopropionate 4-Methylbenzyl Mercaptan 2-Methyl-1-butanethiol 1-Octadecanethiol tert-Octanethiol 1-Octanethiol 1-Pentadecanethiol

Unit Size 25mL 5g 25mL 25mL 25mL 5mL 25mL

25g

25mL 5g 25mL 25g 10g 25mL 25mL 25mL 25mL 5g 5g 5g 100g

25mL 100mL 25g 10mL 5g 25g 25mL

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

25g 500mL 25g 500mL 500mL 500mL 25mL 500mL 1g 5g 500mL 25g 500mL 500g 25g 500mL 500mL 250mL 500mL 25g 25g 25g 500g 25mL 500mL 500g 25mL 25g 400g 5mL 500mL 10mL

Self-Assembled Monolayer (SAM) Forming Agents

Product Name

P0861 P0053 P1715 P0488 T0082 T2972 U0066

Pentafluorobenzenethiol 1-Pentanethiol 2-Phenylethanethiol 1-Propanethiol 1-Tetradecanethiol 4-(Trifluoromethyl)benzenethiol 1-Undecanethiol

Unit Size 5g 25g 25mL 500mL 5g 25g 25mL 500mL 25mL 1g 5g 5mL

B4848 O

O

Br(CH2)3 P OH

HO P (CH2)4

OH

H1459

H1535

CH3(CH2)6

O0371

P OH

O0380

P OH

O

CH3(CH2)7

OH

O (CH2)6

OH

P OH

P OH OH

P OH

OH

N1025

O CH3O

P

OH OH

P2303 O

HO P (CH2)5 OH

O P OH OH

HO HO

CH3(CH2)9 P OH

OH

OH

P2300 O

O CH3(CH2)17

O

O

M1155

HO P

OH

OH

OH

H1536 O

O CF3(CF2)7CH2CH2 P OH

D3884

Materials Chemistry

B1591

Phosphonic Acids

Synthetic Organic Chemistry

Product No.

O CH3(CH2)8

P OH OH

U0088

O

O

P

P

OH OH

O CH3(CH2)10

P OH OH

X0074 O CH2 P

CH2 P O

OH OH

OH OH

Product No.

Product Name

B1591 B4848 D3884 H1459 H1535 H1536 M1155 N1025 O0371 O0380 P2300 P2303 U0088 X0074

(3-Bromopropyl)phosphonic Acid 1,4-Butylenediphosphonic Acid Decylphosphonic Acid (1H,1H,2H,2H-Heptadecafluorodecyl)phosphonic Acid Heptylphosphonic Acid 1,6-Hexylenediphosphonic Acid 4-Methoxyphenylphosphonic Acid Nonylphosphonic Acid Octadecylphosphonic Acid n-Octylphosphonic Acid 1,5-Pentylenediphosphonic Acid 1,4-Phenylenediphosphonic Acid Undecylphosphonic Acid p-Xylylenediphosphonic Acid

Unit Size 1g 1g 1g

1g 1g 200mg 1g 1g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

5g 1g 5g 200mg 5g 1g 1g 1g 5g 5g 1g 1g 5g 5g

315

Materials Chemistry

Synthetic Organic Chemistry

Polymers

Polymers Polyvinyl chloride and polyethylene polymers have long been the mainstay of industrial polymers but are now making way for new high performance polymers. Engineering plastics are polymers engineered to have various specific properties. For example, some polymers are designed for thermal resistance, such as polyamide and polycarbonate, and are widely used. The thermal resistance of a polymer is determined by the softening point: an increase in the softening point increases the material strength. Engineering plastics such as polysulfone, polyether sulfone, polyarylate and polyimide have been developed to improve the softening point and material strength. The softening points of these polymers are all above 150 ºC, and these polymers are incorporated into, for example, firefighter uniforms and bulletproof vests. R&D into engineering plastics continues to further improve their performance. There has also been extensive research into adding new functions to polymers, such as electrical, optical, medical and biological properties. For example, copolymers obtained by the polymerization of fluorine-containing monomers and a variety of other monomers are used to make photoresists, optical fiber dressings, oxygen enrichment membranes, and membrane oxygenators. The maximum absorbance of polysilane is in the ultraviolet region, and it is photosensitive; therefore, polysilane can be used as a positive-type resist with excellent oxygen plasma resistance. Another polymer, polylactic acid (PLA), has been commercialized as an environmentally-friendly polymer that reduces the consumption of fossil fuel resources because it is made from biomass raw materials. There are many broad applications of polymer materials, making R&D in this field highly promising. The page below describes natural polymers, semisynthetic polymers and synthetic polymers.

Natural Polymers Product No. A0733 A0456 A0847 A1328 A0738 C1805 C1804 C2871 C0072 C2395 C2396 C0831 C0335 D3672 D1448 D1449 G0331 H0393 H0595 I0041 L0082 L0045 P0024 H0652 H0603 L0098 X0048 Z0008

316

Product Name Alginic Acid Amylopectin Hydrate (Amylose free), from Waxy Corn Amylose (Mw.=ca. 15,000) (+)-Arabinogalactan from Larch Wood Calcium Alginate ι-Carrageenan κ-Carrageenan λ-Carrageenan Chitin Chitosan (5-20mPa・s, 0.5% in 0.5% Acetic Acid at 20℃) Chitosan (50-100mPa・s, 0.5% in 0.5% Acetic Acid at 20℃) Chitosan (200-600mPa・s, 0.5% in 0.5% Acetic Acid at 20℃) Chondroitin Sulfate Sodium Salt Dermatan Sulfate Sodium Salt Dextran 40 (Mw.=ca. 40,000) Dextran 70 (Mw.=ca. 70,000) Glucan from Black Yeast Heparin Sodium Salt from Hog intestine Hyaluronic Acid from Cockscomb Inulin Lignin (Alkaline) Lignin (Dealkaline) Pectin from Citrus Potassium Hyaluronate from Cockscomb Sodium Hyaluronate from Cockscomb Sodium Ligninsulfonate Xanthan Gum Zymosan

Unit Size 25g 25g

25g 25g 25g 1g 25g 25g 25g 25g 25g 20mg 25g 25g 100g 1g 100mg 5g 25g 25g 25g 100mg 25g 25g 100mg

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

500g 500g 1g 25g 500g 500g 500g 5g 250g 500g 100g 500g 100g 100mg 500g 500g 5g 1g 1g 25g 500g 500g 500g 1g 1g 500g 500g 1g

Polymers

Product Name

C0045 C0603 E0265 E0072 E0266 E0290 H0242 H0418 H0392 H0473 H0474 H0386 H0475 M0290 M0291 M0292 M0293 M0294 M0185 M0295

Carboxymethyl Cellulose Sodium n≈500 Carboxymethyl Cellulose Sodium n≈1050 Ethyl Cellulose [9-11mPa・s, 5% in Toluene + Ethanol (80:20) at 25℃] Ethyl Cellulose [18-22mPa・s, 5% in Toluene + Ethanol (80:20) at 25℃] Ethyl Cellulose [45-55mPa・s, 5% in Toluene + Ethanol (80:20) at 25℃] Ethyl Cellulose [90-110mPa・s, 5% in Toluene + Ethanol (80:20) at 25℃] Hydroxyethyl Cellulose (200-300mPa・s, 2% in Water at 20℃) Hydroxyethyl Cellulose (800-1,500mPa・s, 2% in Water at 20℃) Hydroxyethyl Cellulose (4,500-6,500mPa・s, 2% in Water at 25℃) Hydroxypropyl Cellulose (3-6mPa・s, 2% in Water at 20℃) Hydroxypropyl Cellulose (6-10mPa・s, 2% in Water at 20℃) Hydroxypropyl Cellulose (150-400mPa・s, 2% in Water at 20℃) Hydroxypropyl Cellulose (1,000-4,000mPa・s, 2% in Water at 20℃) Methyl Cellulose (13-18mPa・s, 2% in Water at 20℃) Methyl Cellulose (20-30mPa・s, 2% in Water at 20℃) Methyl Cellulose (80-120mPa・s, 2% in Water at 20℃) Methyl Cellulose (350-550mPa・s, 2% in Water at 20℃) Methyl Cellulose (1,000-1,800mPa・s, 2% in Water at 20℃) Methyl Cellulose (3,500-5,600mPa・s, 2% in Water at 20℃) Methyl Cellulose (7,000-10,000mPa・s, 2% in Water at 20℃)

Unit Size 25g 25g 25g 25g 25g 25g 25g 25g 25g 25g 25g 25g 25g 25g 25g 25g 25g 25g 25g 25g

500g 500g 500g 500g 500g 500g 500g 500g 500g 500g 500g 500g 500g 500g 500g 500g 500g 500g 500g 500g

Materials Chemistry

Product No.

Synthetic Organic Chemistry

Semisynthetic Polymers

Synthetic Polymers Product No.

Product Name

A0140 A0259 A0260 G0264 M0086 M0088 S0098 P0840 H0543 N0443 P1187 P2034 P0885 P0903 P2241 P0872 P2183 P2184 P2185 P2186 P2187 P0704 P0707 P0708 P0709 P0710 P0467 P0381 P2018 P0384 S0099 P0966 P0469 P0804 P0656 P0641 P1007 P0691

Acrylamide Polymer (Mw.=400,000-800,000) (containing small amounts of formalin as fungicide) (10% in Water) 3-Aminobenzaldehyde Polymer 4-Aminobenzaldehyde Polymer Ethyl Glyoxylate Polymer form (47% in Toluene) 25g 100g Isobutyl Methacrylate Polymer 25g Methyl Methacrylate Polymer 25g Poly(diethylene Glycol Succinate) Polyethylene Glycol 200 25g Polyethylene Glycol 300 25g Polyethylene Glycol 400 25g Polyethylene Glycol 600 25g Polyethylene Glycol 2,000 25g Polyethylene Glycol 4,000 25g Polyethylene Glycol 6,000 25g 25g Polyethylene Glycol Dimethyl Ether (Mw.=ca. 240) Polyethylene Glycol Monolaurate n≈10 25g Polyethylene Glycol Monomethyl Ether 400 100g Polyethylene Glycol Monomethyl Ether 550 100g Polyethylene Glycol Monomethyl Ether 1000 100g Polyethylene Glycol Monomethyl Ether 2000 100g Polyethylene Glycol Monomethyl Ether 4000 100g Polyethylene Glycol Mono-4-nonylphenyl Ether n≈2 Polyethylene Glycol Mono-4-nonylphenyl Ether n≈10 Polyethylene Glycol Mono-4-nonylphenyl Ether n≈15 Polyethylene Glycol Mono-4-nonylphenyl Ether n≈18 Polyethylene Glycol Mono-4-nonylphenyl Ether n≈20 Poly(ethylene Glycol Succinate) Polyethyleneimine (ca. 30% in Water) 25g Poly(3-hexylthiophene-2,5-diyl) (regioregular) 200mg 25g Poly(methyl Vinyl Ether) (30% in Water) Poly(neopentyl Glycol Succinate) 5g Poly(perfluoropropylene Oxide) Poly(vinyl Alcohol) n=1750±50 25g Poly(vinyl Alcohol) n≈2,000 (degree's of saponification ca. 80mol%) 25g 5g Poly(N-vinylcarbazole) Polyvinylformal 25g Poly(vinyl Methyl Ether) (50% in Methanol) Polyvinylpyrrolidone (insoluble)

Unit Size

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

500g 25g 25g 500g 500g 500g 25g 500g 500g 500g 500g 500g 500g 500g 500g 500g 500g 500g 500g 500g 500g 25g 25g 25g 25g 25g 25g 500g 1g 500g 25g 10g 500g 500g 25g 500g 500g 100g

317

Product No.

Product Name

P0471 P0472 P0696 P0473 P0385 P0382

Polyvinylpyrrolidone K 15 Viscosity Average Molecular Wt. 10,000 Polyvinylpyrrolidone K 30 Viscosity Average Molecular Wt. 40,000 Polyvinylpyrrolidone K 60 Viscosity Average Molecular Wt. 160,000 (ca. 35% in Water) Polyvinylpyrrolidone K 90 Viscosity Average Molecular Wt. 360,000 Poly(1-vinylpyrrolidone-co-Vinyl Acetate) (Copolymer, 3:7) (50% in Ethanol) Poly(1-vinylpyrrolidone-co-Vinyl Acetate) (Copolymer, 7:3) (50% in Ethanol)

Unit Size 25g

100g 25g 25g 25g 25g 25g

Materials Chemistry

Synthetic Organic Chemistry

Polymers

318

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

500g 500g 500g 500g 500g 500g

Monomers

Monomers are the building blocks of polymers and are categorized below. Lists of categorized monomers also appear on our website.

Ethylene Monomers Styrene Monomers

Synthetic Organic Chemistry

Monomers

Acrylate Monomers Methacrylate Monomers Materials Chemistry

Acrylamide Monomers Methacrylamide Monomers Divinyl Monomers, Diallyl Monomers Cyclic Olefin Monomers Epoxide Monomers Diol Monomers Diamine Monomers Tetracarboxylic Dianhydride Monomers Dicarboxylic Acid Monomers Diacid Chloride Monomers Bismaleimide Monomers Isocyanate Monomers Thiol Monomers Lactone, Lactide Monomers etc.

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

319

Materials Chemistry

Synthetic Organic Chemistry

Polymerization Inhibitors

Polymerization Inhibitors Monomers are often stabilized by the addition of inhibitors to prevent polymerization initiation by light, heat and air. For example, stable radical compounds which can trap free radicals are used to inhibit radical polymerization.

B0887

B0833 O

B0739 OH

D0228 OH

CH3

OH

C CH3 CH3 O

H0186

CH3 C CH3

OH

CH3

M0123

CH3 CH3

D4313 OH

CH3

C

C CH3

CH3

CH3

O2N N N

NO2

O2N

CH3

P0106 OH

OH

H N

OCH3

OH

320

Product No.

Product Name

B0887 B0833 B0739 D0228 D4313 H0186 M0123 P0106

1,4-Benzoquinone tert-Butylhydroquinone 4-tert-Butylpyrocatechol 2,6-Di-tert-butyl-p-cresol 1,1-Diphenyl-2-picrylhydrazyl Free Radical Hydroquinone 4-Methoxyphenol Phenothiazine

S

Unit Size

25g

25g 25g 25g 25g 1g 25g 100g 25g

The chemical, physical and toxicological properties of some chemicals have not been thoroughly investigated. Please handle with care.

500g 500g 500g 500g 5g 500g 500g 500g

Polymerization Initiators

Initiators are often used in chain-growth polymerization such as radical polymerization to regulate initiation by heat or light. Thermal polymerization initiators are compounds that generate radicals or cations upon exposure to heat. For example, azo compounds such as 2,2'-azobis(isobutyronitrile) (AIBN) and organic peroxides such as benzoyl peroxide (BPO) are well-known thermal radical initiators, and benzenesulfonic acid esters and alkylsulfonium salts have been developed as thermal cation initiators. Photopolymerization initiators are roughly categorized into three groups depending on the generated active species (radicals, cations, anions). Conventional photopolymerization initiators such as benzoin derivatives generate free radicals upon light irradiation. Photo-acid generators which produce cations (acid) upon light irradiation found practical use in the late 1990s. Photo-base generators, which produce anions (base) upon light irradiation, are of current research interest.

Synthetic Organic Chemistry

Polymerization Initiators

Materials Chemistry

A1671

Thermal Polymerization Initiators

A0566

A1670 CH3

CH3

NC C N N C CN CH3

C2223

A2735

CH3

CH3

CH3CH2 C N N C CH2CH3 CN

CH3

CH3

CH3 C O O C CH3 CH3

CH3

CH3

CH3

NH CH3

CH3 NH

CH3

CH3

C NH2

. 2HCl

O

CH3 CH3

CH3 CHCH2

CH3

C N N C CN

CH2CH

CN

CH3 CH3

B3153

O

O

C O O C

CH3 CH3 C OOH CH3

D3797 CH3

C OOH

O

HO C CH2CH2 C N N C CH2CH2 C OH CN CN

B3152

H2 N C C N N C

CN

D3411 CH3

Thermal Radical Initiators

A0680

CH3

O CH3

CH3 O

CH3O C C N N C CH3

C OCH3

CH3

Product No.

Product Name

A1671 A0680 A0566 A1670 A2735 B3152 B3153 C2223 D3411 D3797

4,4'-Azobis(4-cyanovaleric Acid) (contains ca. 20% Water) 2,2'-Azobis(2,4-dimethylvaleronitrile) 2,2'-Azobis(isobutyronitrile) 2,2'-Azobis(2-methylbutyronitrile) 2,2'-Azobis(2-methylpropionamidine) Dihydrochloride Benzoyl Peroxide (wetted with ca. 25% Water) tert-Butyl Hydroperoxide (70% in Water) Cumene Hydroperoxide (contains ca. 20% Aromatic Hydrocarbon) Di-tert-butyl Peroxide Dimethyl 2,2'-Azobis(2-methylpropionate)

Unit Size 25g 25g 25g 25g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

250g 500g 500g 500g 25g 25g 100g 100g 100mL 25g

321

Polymerization Initiators

Materials Chemistry

Synthetic Organic Chemistry

C2363

Thermal Cationic Initiators

C0454

D2685 NH

O CH3

NC

S O O

Product No.

Product Name

C2363 C0454 D2685

Cyclohexyl p-Toluenesulfonate Dicyandiamide Diphenyl(methyl)sulfonium Tetrafluoroborate

N H

CH3

NH2

BF4

S

Unit Size 5g 25g 1g

A0061

B3633

B0221 B0050

N

C C

Cl3C

O CH3O

B1019

N N

O O

C CH3

B0222 B0079

CCl3 O O

A1028

Photo-Radical Initiators

Photopolymerization Initiators

O

25g 500g 5g

C C

OCH3

B1015

OH O

O

O

CH C

CH C

CH C

OCH2CH3

OCH2CH(CH3)2

O

B0942

B0869

B0083

B0103

O

O

O

CH C

CH C

C

OCH(CH3)2

OCH3

B3914

B1164 O C

O

O

C

C OH

COOH

B1225

B0139

B0481

D4196

Cl O N(CH3)2 O

N

O

N

N

C C CH2

N N

CH2CH3

Et2N

O

C

NEt2

Me2N

C

NMe2

O

O

C

C

Cl

D1621

D1640

D2375

D1702

D3358 O

O Cl

C

Cl

P

O OCH3

CH2CH3

O OCH2CH3

O

C C

C CH OCH2CH3

S

C O CH3

CH3

OCH3 CH2CH3 CH3

E0063

H0617

H1361

H0991

P0211

O CH2CH3

O OH C

O OH

O NOH

C C CH3

C C CH3

OH

C C CH3

CH3

O CH3 HOCH2CH2O

O

322

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Polymerization Initiators

B1231

M2028

P1410

Synthetic Organic Chemistry

O

O

CH3 O

C

O

N C

C CH

C

SCH3

O

CH3

COOCH3

CH3

SO2

Product Name

A0061 A1028 B0221 B0050 B3633 B0222 B0079 B1019 B1015 B0942 B0869 B0083 B0103 B1164 B3914 B1225 B0139 B0481 D4196 D1621 D1640 D2375 D1702 D3358 E0063 H0617 H1361 H0991 P0211 B1231 M2028 P1410

Acetophenone p-Anisil Benzil Zone Refined (number of passes:22) Benzil 2-(1,3-Benzodioxol-5-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine Benzoin Zone Refined (number of passes:40) Benzoin Benzoin Ethyl Ether Benzoin Isobutyl Ether Benzoin Isopropyl Ether Benzoin Methyl Ether Benzophenone 2-Benzoylbenzoic Acid 4-Benzoylbenzoic Acid 2-Benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone 2,2'-Bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole 4,4'-Bis(diethylamino)benzophenone 4,4'-Bis(dimethylamino)benzophenone 1,4-Dibenzoylbenzene 4,4'-Dichlorobenzophenone 2,2-Diethoxyacetophenone 2,4-Diethylthioxanthen-9-one 2,2-Dimethoxy-2-phenylacetophenone Diphenyl(2,4,6-trimethylbenzoyl)phosphine Oxide 2-Ethylanthraquinone 1-Hydroxycyclohexyl Phenyl Ketone 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone 2-Hydroxy-2-methylpropiophenone 2-Isonitrosopropiophenone Methyl 2-Benzoylbenzoate 2-Methyl-4'-(methylthio)-2-morpholinopropiophenone 2-Phenyl-2-(p-toluenesulfonyloxy)acetophenone

Unit Size

B2380

Photo-Cationic Initiators

D2248

B2381

tBu

tBu

I

tBu

25g

25g

25g 25g

D2238

CCl3

tBu

BF4

CF3SO3

D2253

F0362

AsF6

N O

PF6

CF3SO3

N Cl3C

OCH3

N N

CH CH

OCH3

I

CH3

I0591

I

I

5g 25g

25g 25g 25g 100g

D2963

CCl3

I

25g

25g 25g 25g 100g

25g 25g

S PF6

25g 100g 25g 25g 25g 25g 25g 5g 25g

25g

C1390

I

500g 25g 1sample 500g 5g 1sample 500g 500g 500g 500g 500g 500g 500g 25g 100g 25g 500g 500g 5g 500g 500g 250g 500g 25g 500g 500g 100g 500g 25g 500g 500g 1g

Materials Chemistry

Product No.

CH

CH

CH3 CH3

CH

N N

F

F

F

F 4

B

F

CCl3

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

323

Polymerization Initiators

Synthetic Organic Chemistry

M1245

M1209

N0137

T1609

CCl3 N

N CH3

Cl3C

N N

CCl3

N

T1608

O

CH

CH

N

N

BF4

N

Br

S

BF4

S

CCl3

OCH3

T2041

NO2

T2042 CH3

CH3

S

S

PF6 CH3

Materials Chemistry

CH3

CH3

CH3

CF3SO3

Product No.

Product Name

B2380 B2381 C1390 D2963 D2248 D2238 D2253 F0362 I0591 M1245 M1209 N0137 T1609 T1608 T2041 T2042

Bis(4-tert-butylphenyl)iodonium Hexafluorophosphate Bis(4-tert-butylphenyl)iodonium Trifluoromethanesulfonate Cyclopropyldiphenylsulfonium Tetrafluoroborate 2-(3,4-Dimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine Diphenyliodonium Hexafluoroarsenate Diphenyliodonium Hexafluorophosphate Diphenyliodonium Trifluoromethanesulfonate 2-[2-(Furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine 4-Isopropyl-4'-methyldiphenyliodonium Tetrakis(pentafluorophenyl)borate 2-(4-Methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine 2-[2-(5-Methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine 4-Nitrobenzenediazonium Tetrafluoroborate Triphenylsulfonium Bromide Triphenylsulfonium Tetrafluoroborate Tri-p-tolylsulfonium Hexafluorophosphate Tri-p-tolylsulfonium Trifluoromethanesulfonate

Unit Size

A2502

Photo-Anionic Initiators

N0528

O

CH3

C ON C

1g

5g 1g 5g 5g

100mg

1g 1g 1g

5g 1g 1g 5g 1g 25g 5g 5g 25g 25g 5g 25g 5g 5g 1g 5g

O0396 NO2 O

O CH3O CH3

324

1g

OCH3 N H

O

CH3 O

O

O

H N

H N N

CH3

Product No.

Product Name

A2502 N0528 O0396

Acetophenone O-Benzoyloxime Nifedipine 2-(9-Oxoxanthen-2-yl)propionic Acid 1,5,7-Triazabicyclo[4.4.0]dec-5-ene Salt

Unit Size 1g 10g

5g 25g 1g

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Polymerization Catalysts

The Zieglar-Natta catalyst discovered in 1953 made possible the synthesis of high-density polyethylene. Later, transition metal catalysts such as metallocene were developed for polyolefin synthesis. Transition metal carbene complexes were used as catalysts for ring-opening metathesis polymerization in Nobel Prize-winning work in 2005. This section also includes catalysts for Kumada-Tamao-Corriu cross coupling for polymer synthesis.

Olefin Polymerization Catalysts

D3307

D3321

Metallocene Catalysts

C1995

Cl

Ti

Cl

Cl

Cl

D4100

Zr

Materials Chemistry

C1994

Cl

Cl

D3286

H0914

CH3 CH3 CH3

CH3 CH3

Cl

Zr Cl

CH3 CH3

CH3 CH3

(CH2)3CH3 Cl

Zr

CH2CH2CH3

Cl

CH3 Ti

CH3

Cl

Hf

Cl

Cl

Hf

Cl

Cl

Ti

Cl

CH2CH2CH3

(CH2)3CH3

CH3

I0646

I0645

P1651

C1411

T0616

CH3 CH3 Ti

Cl

Cl

CH3

C

Zr

Cl Cl

CH3

Cl

Cl

V0090

Z0010

Cl

CH3

CH3

V Cl

Ti Cl

CH3

Ti

Cl

Al

CH3 CH3

Cl

Z0007

H

Zr

Cl

Cl

Zr

Cl

Product No.

Product Name

C1994 C1995 D3307 D3321 D4100 D3286 H0914 I0646 I0645 P1651 C1411 T0616 V0090 Z0010 Z0007

Cyclopentadienyltitanium(IV) Trichloride Cyclopentadienylzirconium(IV) Trichloride Decamethylzirconocene Dichloride 1,1'-Dibutylzirconocene Dichloride Dimethyltitanocene (5% in Tetrahydrofuran/Toluene) 1,1'-Dipropylhafnocene Dichloride Hafnocene Dichloride (Indenyl)titanium(IV) Trichloride 1,1'-Isopropylidenezirconocene Dichloride (Pentamethylcyclopentadienyl)titanium(IV) Trichloride Tebbe Reagent (ca. 0.5mol/L in Toluene) Titanocene Dichloride Vanadinocene Dichloride Zirconocene Chloride Hydride Zirconocene Dichloride

Unit Size 1g 1g 1g

1g

5g

5g 1g

5g 5g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

Synthetic Organic Chemistry

Polymerization Catalysts

5g 5g 1g 5g 100g 1g 25g 1g 100mg 1g 25mL 25g 1g 25g 25g

325

Polymerization Catalysts

Synthetic Organic Chemistry

D4404

T2863

T2313 F

Olefin Polymerization Co-catalysts

F

F NH

F

B F

F

CH3 CH3

F

B F

F 4

F

F

F

C

F F

F F

4

F

B F F

F

F

Product No.

Product Name

D4404 T2863 T2313

N,N-Dimethylanilinium Tetrakis(pentafluorophenyl)borate Triphenylmethylium Tetrakis(pentafluorophenyl)borate Tris(pentafluorophenyl)borane

F F F F

Unit Size 200mg 1g 1g

1g 5g 5g

Materials Chemistry

P1427

Olefin Metathesis Catalysts

CH3

O O PEG O C (CH2)2 C O

O Ru

CH CH3 Cl Cl

P

Product No.

Product Name

P1427

Polyethylene Glycol-bound Ruthenium Carbene Complex

Unit Size

B3235

100mg

B2225

B1313

(CH3)2CH

Ph

Cross-coupling Polymerization Catalysts

B3161

(CH3)2CH

CH(CH3)2 N Ni Cl Cl PPh3 CH(CH3)2

Ni

P Ph

Ph

Ph P

Ph

Ph P

Cl

Cl Ni

Cl

Cl

P Ph

Ph

T1350

t-Bu3P

Pd

P

t-Bu3P

326

N

3

Pd 4

Product No.

Product Name

B3235 B2225 B1313 B3161 T1350

[1,3-Bis(2,6-diisopropylphenyl)imidazol-2-ylidene]triphenylphosphine Nickel(II) Dichloride 200mg [1,2-Bis(diphenylphosphino)ethane]nickel(II) Dichloride 1g 5g [1,3-Bis(diphenylphosphino)propane]nickel(II) Dichloride 5g 250mg Bis(tri-tert-butylphosphine)palladium(0) Tetrakis(triphenylphosphine)palladium(0) 1g 5g

Unit Size 1g 25g 25g 1g 25g

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Polymerization Catalysts

B1291

CH3

D0302

CH3

N

N

O

(CH2)3CH3

CH2N

CH3

P0881 CH3

CH3

N

CH3 CH3

T0537

T1598 CH3

CH3

N CH3

N

CH3

N

Z0006

N CH3

CH3 N CH3

O

N

OH

CH3

OH

T1289 CH3

CH3

O Zr

CH3

O CH3

N

N

CH3

CH3 4

T1618

CH3

CH3 CH3

CH3 N

CH3

CH3 N

Materials Chemistry

D0705

CH3

(CH2)3CH3

N

D1756

(CH2)10CH3

CH3(CH2)10 C O Sn (CH2)3CH3

(CH2)3CH3

D0688

O C

N

N O

O

O C CH3

C O Sn

O

N O

D0649

O CH3

CH3

D0303

O

N

N

O

D1313

Synthetic Organic Chemistry

CH3

Polyurethane Catalysts

D0134

B1784

O

N

OH

CH3

CH3

CH3

CH3

N

N

N

CH3

Product No.

Product Name

B1291 B1784 D1313 D0134 D0302 D0303 D0649 D1756 D0688 D0705 P0881 Z0006 T1289 T0537 T1598 T1618

Bis(2-dimethylaminoethyl) Ether Bis(2-morpholinoethyl) Ether 1,5-Diazabicyclo[4.3.0]-5-nonene 1,4-Diazabicyclo[2.2.2]octane Dibutyltin Diacetate Dibutyltin Dilaurate 2-(Dimethylamino)ethanol 2-[2-(Dimethylamino)ethoxy]ethanol N,N-Dimethylbenzylamine N,N-Dimethylcyclohexylamine N,N,N ',N '',N ''-Pentamethyldiethylenetriamine Tetrakis(2,4-pentanedionato)zirconium(IV) N,N,N ',N '-Tetramethyl-1,4-diaminobutane N,N,N ',N '-Tetramethyl-1,6-diaminohexane N,N,N '-Trimethyl-N '-(2-hydroxyethyl)bis(2-aminoethyl) Ether 2,6,10-Trimethyl-2,6,10-triazaundecane

Unit Size 10mL 25g 25g 25g

25mL 25g 25mL 100g 100g 100g 25mL 25mL 25mL 25mL 25mL 25g

500mL 500g 250mL 500g 500g 500g 500mL 500mL 500mL 500mL 500mL 500g 25mL 25mL 500mL 25mL 500mL 25mL 500mL

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

327

Precise Polymerization Reagents In the radical, cationic or anionic polymerization of vinyl monomers, the chain propagation is often compromised by termination reaction, chain-transfer reaction, and other side reactions. There has been much research on living polymerization, which decreases termination reaction and maintains actively growing polymer chains, allowing control of the average molecular weight and thus synthesis of polymers with a narrow molecular weight distribution.

B0643

Materials Chemistry

Synthetic Organic Chemistry

Precise Polymerization Reagents

Atom Transfer Radical Polymerization (ATRP) Reagents

B0592

B0607

B1058

CH2

Initiators

B3500

Br

Br

C0094

C0166

Br CH

CH3 O

CH3 O

CH3 Br

C Br

C

Br

C

D1122

B0532

CH3

CH3

C O C CH3

CH3

CH3

B0606

ClCH2CN

B0533

B1460

Br

Br

C0093

328

O

C

CH3

C1633

OCH3

Br

OCH3

Product No.

Product Name

B0643 B1058 B0592 B0607 B3500 C0094 C0166 D1122 B0532 B0606 B0533 B1460 C0093 C1633

Allyl Bromide Bromoacetonitrile (1-Bromoethyl)benzene 2-Bromoisobutyryl Bromide tert-Butyl 2-Bromoisobutyrate Chloroacetonitrile (1-Chloroethyl)benzene 2,2-Dichloroacetophenone Ethyl Bromoacetate Ethyl 2-Bromoisobutyrate Methyl Bromoacetate Methyl 2-Bromopropionate Methyl Chloroacetate Methyl (R)-(+)-2-Chloropropionate

OCH3 Br

C0970 O

O

Cl

CH3 OCH3

CH3

C1634

CH3

O

O

C OCH2CH3

O

O Cl

CH3 O

O

Cl

CH3

O C CHCl2

CN

CH3

OCH3 Cl

CH3

OCH3 Cl

Unit Size 25g

25g

25g 25g

25g 500g 100g 500g 25g 100g 25g 500g 25g 500g 100g 500g 25mL 500mL 25g 25g 500g 100g 500g 100g 500g 25g 500g 25mL 500mL 5g

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Precise Polymerization Reagents

Product Name

C1634 C0970

Methyl (S)-(-)-2-Chloropropionate Methyl 2-Chloropropionate

Unit Size

B0468

5g 25mL 500mL

B2709

D3134 CH3

Ligands N

CH3

CH3

C(CH3)3 C(CH3)3

OCH3

OCH3

PPh2

N

N

N

D3242

N

D2471

(CH2)8CH3 (CH2)8CH3

P0881

O C OH

P

P N

N

N

T1597

NH

T1487 (CH2)3CH3

HN

CH3(CH2)3 P

NH

HN

OCH3 CH3O

P

N N

N

N

HN

N N

Bu

H N

CH3 CH3

N CH3

P Bu

T0861 CH3

CH3

CH3 N CH3

N CH3

Bu

NH

T2898

P

CH3 N

T0361

CH2

T0519

N

OCH3

CH2 N CH2CH2 N

CH2

T1879 CH3

T1878

CH2

(CH2)3CH3 Br

(CH2)3CH3

T0488

N

N

T1124

CH3

N

N

OCH3

CH3

N

CH3

CH3

P CH3O

OCH3

T2671 CH2 N N

N CH2 CH2

N

Product No.

Product Name

B0468 B2709 D3134 D3886 B0852 D3917 D3242 D2471 P0881 T1597 T1124 T1487 T1878 T0361

2,2'-Bipyridyl 4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene 4,4'-Di-tert-butyl-2,2'-bipyridyl 4,4'-Dimethoxy-2,2'-bipyridyl 4,4'-Dimethyl-2,2'-bipyridyl 4,4'-Dinonyl-2,2'-bipyridyl 2-(Diphenylphosphino)benzoic Acid Diphenyl-2-pyridylphosphine N,N,N ',N '',N ''-Pentamethyldiethylenetriamine 1,4,8,11-Tetraazacyclotetradecane Tetrabutylphosphonium Bromide N,N,N ',N '-Tetrakis(2-pyridylmethyl)ethylenediamine 1,4,7-Triazacyclononane Tributylphosphine

Unit Size 25g

1g

100g 1g 1g 1g 5g 1g

1g 25mL 1g 25g 100g 1g 200mg 1g 25mL 100mL

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

500g 5g 5g 5g 25g 5g 1g 5g 500mL 5g 500g 5g 5g 500mL

329

Materials Chemistry

D3917 CH3

D3886

O

N PPh2

B0852

Synthetic Organic Chemistry

Product No.

Synthetic Organic Chemistry

Precise Polymerization Reagents

Product No.

Product Name

T0488 T1879 T0519 T2898 T0861 T2671

Trimethyl Phosphite 1,4,7-Trimethyl-1,4,7-triazacyclononane (stabilized with NaHCO3) Triphenylphosphine Tris[2-(dimethylamino)ethyl]amine Tris(4-methoxyphenyl)phosphine Tris(2-pyridylmethyl)amine

Unit Size

B1571

Materials Chemistry

Transition Metal Complexes

C2201

Ph3P Ph3P

Ni

C1592

Cl Cl

Product No.

Product Name

B1571 C2201 C1592 D1997

Bis(triphenylphosphine)nickel(II) Dichloride Cyclopentadienylbis(triphenylphosphine)ruthenium(II) Chloride Cyclopentadienyliron Dicarbonyl Dimer Tris(triphenylphosphine)ruthenium(II) Dichloride

Reversible Addition Fragmentation Chain Transfer (RAFT) Polymerization Reagents

Product No.

Product Name

B0479 B0486 T2401

Tetraethylthiuram Disulfide Tetramethylthiuram Disulfide S-(Thiobenzoyl)thioglycolic Acid

S

CH3

1g

CH3 CH3

S

N C S S C N CH3

S

H0878

N O

330

O

C SCH2 C OH

CH3

A1343

CH3

CH3 CH3

N

CH3

CH3 CH3

M1197

CH3

CH3 N O

CH3

C OH CH3

N

CH3

N

CH3 CH3

CH3 N

CH3

O

O0266

CH3 CH3

O

O

OCH3

500g 500g 25g

C1428 NH2

HN C CH3

O C

CH3

100g 5g 5g 5g

S

CH3

25g 25g 5g

O

CH3

S

CH3 CH 3

O

CH3

Cl

Unit Size

Nitroxide-Mediated Radical Polymerization (NMP) Reagents

CH3

Cl

T2401

N C S S C N

O

CH3

Rh 3

10g 1g

B0486

A1348

OH

P 3

Unit Size

B0479

H0865

D1997

Fe OC CO OC CO Fe

Ph3P Ru PPh3

Cl

25mL 5g 500g 5g 25g 5g

1g 25g 1g 5g 1g

T1560 O

CH3

CH3

CH3

CH3

O

Product No.

Product Name

A1348 A1343 C1428 H0865 H0878 M1197

4-Acetamido-2,2,6,6-tetramethylpiperidine 1-Oxyl Free Radical 4-Amino-2,2,6,6-tetramethylpiperidine 1-Oxyl Free Radical 4-Carboxy-2,2,6,6-tetramethylpiperidine 1-Oxyl Free Radical 4-Hydroxy-2,2,6,6-tetramethylpiperidine 1-Oxyl Free Radical 4-Hydroxy-2,2,6,6-tetramethylpiperidine 1-Oxyl Benzoate Free Radical 4-Methoxy-2,2,6,6-tetramethylpiperidine 1-Oxyl Free Radical

CH3 N O

CH3

CH3 CH3

CH3 N

CH3

O

Unit Size 5g 1g 100mg 5g 1g 1g

25g 5g 1g 25g 5g 5g

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Precise Polymerization Reagents

Product Name

O0266 T1560

4-Oxo-2,2,6,6-tetramethylpiperidine 1-Oxyl Free Radical 2,2,6,6-Tetramethylpiperidine 1-Oxyl Free Radical

Unit Size

D1340

Immortal Polymerization Reagents

5g 5g

Al

CH3

NH

Zn(CH2CH3)2

Cl

25g 25g

T1359

D3902 D3214

CH3

Synthetic Organic Chemistry

Product No.

N

N HN

CH3

Al

Materials Chemistry

T0782 T1575

T0783 T0925

CH3

CH3 CH3

CH3

Al

CH3

Product No.

Product Name

D1340 D3902 D3214 T1359 T0783 T0925 T0782 T1575

Diethylaluminum Chloride (ca. 15% in Hexane, ca. 0.87mol/L) Diethylzinc (ca. 15% in Toluene, ca. 1mol/L) Diethylzinc (ca. 17% in Hexane, ca. 1mol/L) Tetraphenylporphyrin (Chlorin free) Triethylaluminum (15% in Hexane, ca. 1.0mol/L) Triethylaluminum (15% in Toluene, ca. 1.1mol/L) Trimethylaluminum (15% in Hexane, ca. 1.4mol/L) Trimethylaluminum (15% in Toluene, ca. 1.8mol/L)

Unit Size

B2291 F

Group Transfer Polymerization (GTP) Reagents

P1888

T1295

Bu

F

M1199 CH3

CH

SO2CF3

CH3

O Si CH3

CH3

CH3 OCH3

SO2CF3

F

OCH3

CH3 CH3

Si O C CHCH3 CH3

T2392 Bu

KHF2

D1789

F F

100mL 100mL 100mL 500mL 1g 100mL 100mL 100mL 100mL

N Bu Bu

HF2

Si(CH3)3 CF3SO2 N SO2CF3

Product No.

Product Name

B2291 D1789 M1199 P1888 T1295 T2392

1-[Bis(trifluoromethanesulfonyl)methyl]-2,3,4,5,6-pentafluorobenzene Dimethylketene Methyl Trimethylsilyl Acetal 1-Methoxy-1-trimethylsilyloxypropene Potassium Hydrogenfluoride Tetrabutylammonium Bifluoride N-(Trimethylsilyl)bis(trifluoromethanesulfonyl)imide

Unit Size 100mg 5mL 1g 5g 1g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

1g 25mL 5g 500g 25g 5g

331

Precise Polymerization Reagents

Synthetic Organic Chemistry

B2225

B1313 Ph

Catalyst-transfer Polycondensation Reagents

Ni

P Ph

Ph

Ph P

I0543 I0542

Product Name

B2225 B1313 I0543 I0542

[1,2-Bis(diphenylphosphino)ethane]nickel(II) Dichloride [1,3-Bis(diphenylphosphino)propane]nickel(II) Dichloride Isopropylmagnesium Chloride (ca. 11% in Tetrahydrofuran, ca. 1mol/L) Isopropylmagnesium Chloride (ca. 13% in Ethyl Ether, ca. 1mol/L)

P Ph

CH3

Cl

MgCl

Ph

Unit Size 1g

5g 5g

25g 25g 250g 250g

Materials Chemistry

Product No.

CH3

Cl Ni

Cl

Ph

Ph P

Cl

332

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Resin Additives

The addition of additives makes synthetic resin, a polymer material, workable or stable. This section includes plasticizers which improve the workability of resin by increasing flexibility and stabilizers which protect against resin aging caused by radicals.

Plasticizers

B2715

B2714 O

O

C OCH2

C OCH2

Phthalates

B4302

P0297

O

C O(CH2)3CH3

C OCH2CH(CH2)3CH3

O

O

B0737

O

O

O

mixture of branched chain isomers

P0292

C OCH2CH

CH3

C OC9H19 O

O

CH3

C OCH2CH

CH3

O

O

CH2CH3

O

O

C O(CH2)4CH3

C OCH2 C O(CH2)3CH3

(CH2)3CH3 CH2CH3

C O(CH2)3CH3

(CH2)3CH3

C O(CH2)4CH3

O

O

O

P0293

P0296

CH2CH3

P0291

CH3

C OCH2

P1344

P0298

O

O

O

O

O

C O(CH2)3CH3

C O

C OCH2CH3

C O(CH2)5CH3

C OCH2CH(CH3)2

C O(CH2)3CH3

C O

C OCH2CH3

C O(CH2)5CH3

C OCH2CH(CH3)2

O

O

O

O

O

P0299

P0300

P0301

I0157

O

O

C OC9H19

C O(CH2)7CH(CH3)2

C OC9H19

C O(CH2)7CH(CH3)2

O

O

P0303

mixture of branched chain isomers

P0304 C OC9H19

P0302

O

O

O

C OCH(CH3)2

C OCH3

C OCH3

C OCH(CH3)2

O

C OCH3

O

C OCH3

O

P0305

O

P0306

P0307

O

O

O

C O(CH2)7CH3

C O

C OCH2CH2CH3

C O(CH2)7CH3

C O

C OCH2CH2CH3

O

O

O

C OC9H19

O C OC13H27 C OC13H27

O mixture of branched chain isomers

D3248

Materials Chemistry

P0288

E0164

O mixture of branched chain isomers

P0657

O C OC11H23

O

O

C OCH2CH3

C OCH2CH2O(CH2)3CH3

C OC11H23

C OCH2

C

O

O

O

mixture of branched chain isomers

OCH2CH3

C OCH2CH2O(CH2)3CH3 O

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

Synthetic Organic Chemistry

Resin Additives

333

Materials Chemistry

Synthetic Organic Chemistry

Resin Additives

Product No.

Product Name

P0288 B2714 B2715 B4302 P0297 B0737 P0291 P0292 P0293 P0296 P1344 P0298 P0299 P0300 P0301 I0157 P0302 P0303 P0304 P0305 P0306 P0307 D3248 E0164 P0657

Benzyl Butyl Phthalate Benzyl 2-Ethylhexyl Phthalate Benzyl Isononyl Phthalate (mixture of branched chain isomers) Bis(2-ethylhexyl) Isophthalate Bis(2-ethylhexyl) Phthalate Butyl Phthalyl Butyl Glycolate Diamyl Phthalate Dibutyl Phthalate Dicyclohexyl Phthalate Diethyl Phthalate Dihexyl Phthalate Diisobutyl Phthalate Diisodecyl Phthalate (mixture of branched chain isomers) Diisononyl Phthalate (mixture of branched chain isomers) Diisopropyl Phthalate Dimethyl Isophthalate Dimethyl Phthalate Dinonyl Phthalate (mixture of isomers) Di-n-octyl Phthalate Diphenyl Phthalate Dipropyl Phthalate Ditridecyl Phthalate (mixture of branched chain isomers) Diundecyl Phthalate (mixture of branched chain isomers) Ethyl Phthalyl Ethyl Glycolate Phthalic Acid Bis(2-butoxyethyl) Ester

Unit Size

P1021

P0265 O O P OCH2CH O

Phosphates

25g

500g 25g 25g 500g 500g 500g 500g 500mL 500g 500mL 25g 500g 500mL 500g 500mL 500g 500g 500mL 500mL 500g 500mL 500g 500g 500g 25g

25g 25g 25g 100g 25mL 25g 25mL 5g 25g 25mL

25mL 25g 25g 25mL 25mL 25g 25mL 100mL 25g 25g

P0266

P0273 CH3

(CH2)3CH3 CH2CH3

25g

O

CH3

O

CH3(CH2)4O P O(CH2)4CH3 CH3(CH2)3O P O(CH2)3CH3 O(CH2)4CH3

O O P O

O O(CH2)3CH3

CH3

P1331

P0270 CH3

O

P0271

O P O

O

O

CH3CH2O P OCH2CH3

P0268

P0683 O

CH3

P0269 O

OCH3

O

O CH3(CH2)3OCH2CH2O P OCH2CH2O(CH2)3CH3 OCH2CH2O(CH2)3CH3

OCH3

P1022

O

OCH2CH2Cl

O P O

O CH3O P

OCH2CH3

ClCH2CH2O P OCH2CH2Cl (ClCH2)2CHO P OCH(CH2Cl2)2

334

P0272

CH3

OCH(CH2Cl2)2

CH2CH3

O

CH2CH3

CH3(CH2)3CHCH2O P OCH2CH(CH2)3CH3 OCH2CH(CH2)3CH3 CH2CH3

Product No.

Product Name

P0259 P1021 P0265 P0266 P0273 P1331

Cresyl Diphenyl Phosphate (so called) (mixture of analogue) 2-Ethylhexyl Diphenyl Phosphate Triamyl Phosphate Tributyl Phosphate Tricresyl Phosphate (mixture of isomers) Tri-o-cresyl Phosphate

Unit Size 25mL 500mL 25g 500g 25mL 25g 500g 25g 500g 5g 25g

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Resin Additives

Product Name

P0270 P0271 P0272 P0683 P0268 P0269 P1022

Triethyl Phosphate Trimethyl Phosphate Triphenyl Phosphate Tris(2-butoxyethyl) Phosphate Tris(2-chloroethyl) Phosphate Tris(1,3-dichloro-2-propyl) Phosphate Tris(2-ethylhexyl) Phosphate

Unit Size Synthetic Organic Chemistry

Product No.

25g 25g 25g 25g

500g 500g 500g 500g 25g 25g 500g 25mL 500mL

Materials Chemistry

B0881 CH2CH3

O

C OCH2CH(CH2)3CH3 O

CH2CH3

C OCH2CH(CH2)3CH3

Trimellitate

C OCH2CH(CH2)3CH3 CH2CH3

O

Product No.

Product Name

B0881

Tris(2-ethylhexyl) Trimellitate

Unit Size 25mL 500mL

B2716

A0163 CH3

Fatty Acid Esters

CH3

O

O

O

O

O O

O

O

CH3

CH3

O

CH3

O

(CH2)7

O

S0025

O

(CH2)3CH3

OCH2 CH

(CH2)3CH3

(CH2)8

R O C OCH2CH(CH2)3CH3

O

M0009

CH2CH3

CH

C OR

CH2CH3 CH2CH(CH2)3CH3

R=

F0116

O

O

O

(CH2)4 C O R'

CH3

O

O

CH3

CH3

O

O

R, R'=n-C6H13, n-C8H17, n-C10H21

O

CH3

O

CH2CH3

S0023

A0162

M0010

S0024 O

O O

CH3

O

CH3

O O CH3(CH2)3O C

O (CH2)8

C O(CH2)3CH3

CH3

O

O

CH3

O

OCH2CH3

O

OCH2CH3

CH3CH2O C

O (CH2)8

C OCH2CH3

O

O

S0103

A0706 O

CH3

C OCH2CH(CH2)3CH3

A0655 O

OCH2CH(CH2)3CH3

CH2CH3

O

RO C CH

CH2CH3

O

CH2CH3 OCH2 CH

O

A1386

O

CH2CH3

C OCH2CH(CH2)3CH3 O

CH3

M0011

F0117

A0653 A1473

O

O

CH3

O O

A0164

CH3

CH3

O

O O

CH3 CH3

A1387

O C10H21O C

O (CH2)4 C OC10H21

A0654

O R O C

O

O (CH2)4 C O R

R=C9H19 (mixture of branched isomers)

CH3

O

CH3 O

CH3

CH3 O

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

335

Resin Additives

Synthetic Organic Chemistry

A0166

A1308

M0012

S0027

S0028

O O

O

OCH3

CH3O

CH3O

O

O

OCH3

O

CH3O

OCH3

OCH3

O OCH3

O

CH3(CH2)7O C

O (CH2)8

C O(CH2)7CH3

O

A0931

A1388

O0143 O0054 COOCH2CH3

O CH3

O

R O C

O

Materials Chemistry

O

CH3

O

O0055

R, R'=C7H15, C9H19 (mixture of branched isomer)

CH3

Product No.

Product Name

B2716 A0163 A0653 A1473 F0117 M0011 S0025 A1386 A0655 F0116 M0009 S0023 A0162 M0010 S0024 S0103 A0706 A0164 A1387 A0654 A0166 A1308 M0012 S0027 S0028 A0931 O0143 O0054 A1388 O0055

Bis(2-butoxyethyl) Adipate Bis(2-ethylhexyl) Adipate Bis(2-ethylhexyl) Azelate Bis(2-ethylhexyl) Azelate Bis(2-ethylhexyl) Fumarate Bis(2-ethylhexyl) Maleate Bis(2-ethylhexyl) Sebacate Di-n-alkyl Adipate Dibutyl Adipate Dibutyl Fumarate Dibutyl Maleate Dibutyl Sebacate Diethyl Adipate Diethyl Maleate Diethyl Sebacate Diethyl Succinate Diisobutyl Adipate Diisodecyl Adipate Diisononyl Adipate (so called) Diisopropyl Adipate Dimethyl Adipate Dimethyl Azelate Dimethyl Maleate Dimethyl Sebacate Di-n-octyl Sebacate Dipropyl Adipate Ethyl Oleate Ethyl Oleate Heptylnonyl Adipate (so called) Methyl Oleate

COOCH3

O (CH2)4 C O R'

Unit Size 25g 500g 25mL 500mL 25mL 500mL 25mL 25mL 500mL 25mL 500mL 25mL 500mL 25mL 500mL 25mL 500mL 25g 500g 25g 500g 25mL 500mL 25mL 500mL 25mL 500mL 25mL 500mL 25g 500g 25mL 500mL 25mL 500mL 25mL 500mL 25mL 500mL 25mL 500mL 25mL 25mL 500mL 25g 500g 25mL 25mL 5mL 25mL 25mL 500mL 25mL 500mL 25mL 500mL

D1230

D1522

B0828

O

Polyalcohol Ethers, Esters

B0498

O CH3

O

O

CH3(CH2)3

CH3

G0082

B0489

O

C OCH2CH2 O CH2CH2O C

O O

CH3

G0086

O

O

O

(CH2)3CH3

T0364

CH3

O

O

O

CH3

T0923

O CH3

O

CH3O

O

O

OCH3 CH3

OH OH

O O

CH3

336

O

CH3

O O CH3(CH2)2 C OCH

O

CH2O C (CH2)2CH3 O CH2O C (CH2)2CH3

O CH3

O

O

O

O

CH3

O

O

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Resin Additives

B0496

Synthetic Organic Chemistry

O

CH3O

OCH3

O

Product Name

D1230 D1522 B0828 B0489 B0498 G0082 G0086 T0364 T0923 B0496

Diethylene Glycol Diacetate Diethylene Glycol Dibenzoate Diethylene Glycol Dibutyl Ether Diethylene Glycol Diethyl Ether Diethylene Glycol Dimethyl Ether Monoolein Triacetin Tributyrin Triethylene Glycol Diacetate Triethylene Glycol Dimethyl Ether (stabilized with BHT)

Unit Size

A0879

A0822

25mL 25mL 25mL 25mL 25mL 25g 25g 25mL 25g 25g

C0366

500mL 500mL 500mL 500mL 500mL 500g 500g 500mL 500g 500g

Materials Chemistry

Product No.

A0086

O

Hydroxycarboxylic Acid Esters

O CH3

C OCH

(CH2)5CH3

O

CH2CH

C OCH3

CH(CH2)7

CH2 C O(CH2)3CH3 O

O

CH3 C O C C O(CH2)3CH3 O CH2

C0367

C0368

O CH3CH2O C CH2

OH

O

C CH2 C OCH2CH3

O CH3O C CH2

OH

O

O

C CH2 C O(CH2)3CH3 C O(CH2)3CH3

CH3

C O

CH3CH2O C CH2 O

O

O

C CH2

C OCH2CH3

C OCH2CH3 O

C O(CH2)3CH3

C0601 OH

O

C CH2 C OCH3

C OCH2CH3

C OCH3

O

O

Product No.

Product Name

A0879 A0822 C0366 A0086 C0367 C0368 C0601

Methyl O-Acetylricinoleate Tributyl O-Acetylcitrate Tributyl Citrate Triethyl O-Acetylcitrate Triethyl Citrate Trimethyl Citrate Tripropyl Citrate

B0716 SO2NH(CH2)3CH3

Camphor, etc.

O CH3(CH2)3O C CH2

O

OH

O

CH3CH2CH2O C CH2 C CH2 C OCH2CH2CH3 C OCH2CH2CH3 O

Unit Size 25mL 500mL 25mL 500mL 25mL 500mL 25g 500g 25g 500g 25g 25g

C0011

C0010

CH3 O

CH3 CH3

C1251

CH3 O

CH3 CH3

CH3

CH3 CH3

O

relative

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

337

Resin Additives

Synthetic Organic Chemistry

E0187

N0194

CH3

O2N

O S NHCH2CH3 O

Product Name

B0716 C0011 C0010 C1251 E0187 N0194

N-Butylbenzenesulfonamide (±)-Camphor (+)-Camphor (-)-Camphor N-Ethyltoluenesulfonamide (o- and p- mixture) 2-Nitrobiphenyl

Unit Size 25g 25g 25g

500g 500g 500g 5g 500g 500g

25g 25g

Materials Chemistry

Product No.

B1970

B0724

D0299 OH

CH3

Resin Stabilizers

C

CH3

CH3

H N

CH3

C CH2CH3 H3C

CH3(CH2)2CH

C

CH3

OH

C(CH3)3

CH3

CH3

C(CH3)3

CH3

H3CH2C C H3C

OH

OH

D0228

D0940

CH3 CH3

OH

D0303 OH

CH3

C

C CH3

CH3

CH3

C CH3 H3C

CH3

(CH2)10CH3

O

CH3

O S

CH3(CH2)11O

NH

O(CH2)11CH3

CH3

NH CHCH2CHCH3

(CH2)3CH3

H3C

D0812

D3331

O O C

O

CH3(CH2)10 C O Sn (CH2)3CH3

H 3C C CH3

T0205

CH3

OH

D0609

E0237

P0327

B0055

CH3 NH

CH3CH2O

NH

NH

NH

N H

M0215 (CH3)3C

D1781 OH

HO

CH3(CH2)3 CH2CH3

CH3CH2

T0196

CH3(CH2)3

Ni2

N C S 2

O

O

OH

S

CH3 C CH3 CH3

338

CH3

(CH3)3C

O

O

C(CH3)3

(CH3)3C

O

O

C(CH3)3

HO

O

O

O

NH

H3C H3C

T0916

CH3 C CH3 CH3

C10H21O

P

OC10H21

C CH3 OH

(CH3)3C

C(CH3)3

C(CH3)3

O

O

(CH3)3C HO (CH3)3C

CH3

CH2

CH2

CH3 CH2

CH3

C(CH3)3

O

O P

CH3

P1421

(CH3)3C

OC10H21

C O(CH2)17CH3

CH3

H3C C

OH C(CH3)3

T0510

SH

D1644

OH

OH

N H

CH2CH2

CH3 CH3 HO

N

CH3

C(CH3)3

HO

(CH3)3C

T0420

CH

P0197

(CH3)3C

S

NH

CH3

P0932

C(CH3)3

CH2

NH

CH3

O C(CH3)3

P

O

(CH3)3C

C(CH3)3

OH C(CH3)3

C(CH3)3

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Resin Additives

4,4'-Bis(α,α-dimethylbenzyl)diphenylamine 4,4'-Butylidenebis(6-tert-butyl-m-cresol) 2,5-Di-tert-amylhydroquinone 2,6-Di-tert-butyl-p-cresol 2,5-Di-tert-butylhydroquinone Dibutyltin Dilaurate Dibutyltin Maleate (so called) Didodecyl 3,3'-Thiodipropionate N-(1,3-Dimethylbutyl)-N '-phenyl-1,4-phenylenediamine N,N '-Di-2-naphthyl-1,4-phenylenediamine N,N '-Diphenyl-1,4-phenylenediamine 6-Ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline 4-Isopropylaminodiphenylamine 2-Mercaptobenzimidazole 2,2'-Methylenebis(6-tert-butyl-4-ethylphenol) Nickel(II) Dibutyldithiocarbamate Pentaerythritol Tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] N-Phenyl-1-naphthylamine Stearyl 3-(3,5-Di-tert-butyl-4-hydroxyphenyl)propionate 4,4'-Thiobis(6-tert-butyl-m-cresol) Triisodecyl Phosphite (mixture of isomers) Triphenyl Phosphite 2,4,6-Tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)mesitylene Tris(2,4-di-tert-butylphenyl) Phosphite

Unit Size

25g

25g

B3717

B3400 OH

N

UV Absorbents

N

Benzotriazoles

25g 500g 25g 500g 25g 500g 25g 500g 25g 500g 100g 500g 25g 500g 25g 500g 25g 500g 25g 500g 25g 500g 25g 500g 25g 500g 25g 500g 25g 500g 25g 500g 25g 500g 25g 500g 25g 500g 25g 500g 25mL 500mL 25g 500g 25g 500g 100g 500g

CH3

N

C

N

N

CH3 CH3

C

H0559 N N

OH

N

H0718

Cl

N N

CH3 C CH3

OH

CH3

N

OH

CH3 C CH2CH3 CH3

CH3

CH2CH3

CHCH2CH3

H1261

Cl

CH3 C CH3

CH3

H0560

N

CH3

CH3

D1529 N

CH3 C CH3

N

OH

N

CH3 C CH3

CH3

H0719

Materials Chemistry

Product Name

B1970 B0724 D0299 D0228 D0940 D0303 D0304 T0205 D3331 D0812 D0609 E0237 P0327 B0055 M0215 D1781 P0932 P0197 D1644 T0196 T0420 T0510 T0916 P1421

Synthetic Organic Chemistry

Product No.

N N

OH

CH3 C CH3

N

CH3 CH3

C CH3

N

N N

CH3 O O

HO

CH2

CH3

M1259 N N

OH

N

N

N N

OH

OH N N

N

H3C C CH3 CH3 C CH3 (H3C)3CH2C CH2C(CH3)3

CH3

Product No.

Product Name

B3717 B3400 H0719 H0559 H0718 D1529

2-(2H-Benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol 2-(3-sec-Butyl-5-tert-butyl-2-hydroxyphenyl)benzotriazole 2-(5-tert-Butyl-2-hydroxyphenyl)benzotriazole 2-(5-Chloro-2-benzotriazolyl)-6-tert-butyl-p-cresol 2-(3,5-Di-tert-amyl-2-hydroxyphenyl)benzotriazole 2-(3,5-Di-tert-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole

Unit Size 25g 250g Price on request 25g 500g 25g 500g 25g 500g 25g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

339

Materials Chemistry

Synthetic Organic Chemistry

Resin Additives

Product No.

Product Name

H1261 H0560 H0716 M1259

2-[2-Hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole 2-(2-Hydroxy-5-methylphenyl)benzotriazole 2-(2-Hydroxy-5-tert-octylphenyl)benzotriazole 2,2'-Methylenebis[6-(benzotriazol-2-yl)-4-tert-octylphenol]

Unit Size

D0573

D0575

H0266

HO C

HO

O

OH

CH3O

C

500g 500g 500g 500g

H0288

OH

OH

O

Benzophenones

25g 25g 25g 25g

OCH3

HO

O

O

C

C

OCH3

O(CH2)7CH3

T0118 OH

HO O

HO

C

OH

Product No.

Product Name

D0573 D0575 H0266 H0288 T0118

2,4-Dihydroxybenzophenone 2,2'-Dihydroxy-4,4'-dimethoxybenzophenone 2-Hydroxy-4-methoxybenzophenone 2-Hydroxy-4-n-octyloxybenzophenone 2,2',4,4'-Tetrahydroxybenzophenone

Unit Size

B3924

Hindered Amines

340

CH3 CH3

CH3

25g 25g

S0448

CH3

CH3 N

25g

O O O C (CH2)8 C O

CH3 CH3 N CH3 CH3 CH3

CH3

CH3

HN CH3

CH3

P1513

O O O C (CH2)8 C O

CH3 CH3 NH CH3 CH3

T2324 O

CH2 C C O CH3

Product No.

Product Name

B3924 S0448 P1513 T2324

Bis(1,2,2,6,6-pentamethyl-4-piperidyl) Sebacate Bis(2,2,6,6-tetramethyl-4-piperidyl) Sebacate 1,2,2,6,6-Pentamethyl-4-piperidyl Methacrylate (stabilized with MEHQ) 2,2,6,6-Tetramethyl-4-piperidyl Methacrylate

500g 25g 500g 500g 25g

CH3 CH3 N CH3 CH2

O

CH3 CH3

C C O

NH

CH3

CH3 CH3

CH3 CH3

Unit Size 5g

5g 25g 25g 25g

25g 250g 500g 500g

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Photopolymer Research Reagents

A photopolymer is a photosensitive, optically functional polymer material or resin whose properties, such as solubility, are altered by light irradiation. Photopolymers are widely used as photoresist materials during etching in the manufacture of printed circuits and semiconductor integrated circuits. In positivetype photoresist, photoacid generators (PAG) change the solubility of the photopolymer, whereas negative-type photoresist requires photopolymerization initiators for polymerization and curing. This section includes the monomers required to generate photopolymers. Photopolymerization initiators are described on p. 322.

B4269

B1796

A1389 O

CH3

CH2OCH2

CH2O

CH2O

O

OCH2

O

D3380

C

E0909

O

CH3

CH2 CH C O C CH3

CH3

CH3 C C O C CH3 CH3

CH2

CH3

I0638 CH3

CH3 O

O

O

CH2 C C O

CH2

O

CH3

M2260

O

O

D3381

CH2 CH C O

OCH2

CH3

O

M0326

Materials Chemistry

B2108

CH3

M2261

I0617 CH3

CH3 CH3 O relative

CH2 O

CH3 CH3 O relative

CH3 CH2 O

A1551 O CH3

CH3 O O

CH2 CH3

O C CH3 O

CH2

CH3

O O

O

CH

CH2

Product No.

Product Name

B2108 B4269 B1796 A1389 M0326 D3380 D3381 E0909 I0638 I0617 M2260 M2261 A1551

Benzyl Glycidyl Ether 9,9-Bis(4-glycidyloxyphenyl)fluorene 2,2-Bis(4-glycidyloxyphenyl)propane tert-Butyl Acrylate (stabilized with MEHQ) tert-Butyl Methacrylate Monomer (stabilized with MEHQ) Dicyclopentanyl Acrylate (stabilized with MEHQ) Dicyclopentanyl Methacrylate (stabilized with MEHQ) 2-Ethyl-2-methacryloyloxyadamantane (stabilized with MEHQ) Isobornyl Acrylate (stabilized with MEHQ) Isobornyl Methacrylate (stabilized with MEHQ) 2-Methacryloyloxy-2-methyladamantane (stabilized with MEHQ) Mevalonic Lactone Methacrylate (stabilized with MEHQ) 4-Vinylphenyl Acetate (stabilized with TBC)

Unit Size 5g 25g 5g 25g 25g 500g 25mL 500mL 25mL 500mL 25g 500g 25g 500g 5g 25g 500g 25g 500g 5g 1g 5g 25g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

Synthetic Organic Chemistry

Photopolymer Research Reagents

341

Materials Chemistry

Synthetic Organic Chemistry

Macrocycles for Host-Guest Chemistry

Macrocycles for Host-Guest Chemistry Host-compounds recognize and incorporate specific molecules, atoms or ions (guests) into the molecules to form complexes. In the formation of these complexes, a variety of forces such as electrostatic interaction, hydrophobic interaction, hydrogen bonding, etc. are utilized to create high selectivity. Molecular sensors, synthetic enzymes, separation systems, etc. utilize the high guest selectivity of these host compounds. Synthesis of new host compounds with even higher selectivity are currently being developed. For example, Shinkai and co-workers have developed exciting purification techniques for fullerene C60 employing calixarene. According to these techniques, the stirring of crude fullerene and butylcalix[8]arene in toluene causes only C60 to be incorporated in the calixarene to form and precipitate a complex. Filtration and subsequent stirring of the complex in chloroform cause it to decompose to yield C60 of high purity as a precipitate. This method has been reported to be an efficient purification technique in obtaining C60 compared with conventional column purification techniques.

A1603

A1604 O

O

Crown Ethers

O

A1323 O

O

O

O

O

O

O

O

O

O

O

O

O O

O

O

O

C1714

O

O

O

C1942

O

O

O

O O

O

O

Br

O

O

Br

O

C1943

C0858

O

O

O

O

O O

O

C OH

O2N

O HO

O

O

N N

NO2

O

O

O

O2N

HO O

N N

O

O

O

O

O

NO2

O

C1736 O

O

D2744

O O

O

O

O

NH

O

O

O

O

O

O

D2323

O

O

O

342

D2743

O

O

O HN

O

O

O

C0860

C OH

C0859

O O

O

C1713

O

O

O

O

O

O

O

O O

NH2

O

B2181

O

O

O

B1154

O O

O

C CH3

O

B2189 O

O O

O

B2245

O

O

O

NH

O

B1539

C CH3

O

O

O

B1249

O

HN

O

O

O

A1324

O

NH

O

O

O

A1552

A1404

O

HN

NH O

O

O

O

O

HN

NH

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Macrocycles for Host-Guest Chemistry

D2877

D1533

D2878

D1830

O

O

O

O

O

O

O O

N

O

O

O

O

H0932 H N NH

HN

N

O

O

O

O

O

O O

O

C OCH3

T1875

O HO C CH2

N

N

O CH2 C OH

N CH2 C OH O

T1959

O

O

NO2

NH

HN

T1876

O

CH2OH

O O

O

O

NH

HN

NH

HN

N O

T1597

T2540

NH HN

NH

HN

NH HN

NH

HN

T1878

O

T1874 O

O

O

. 4HCl

O

O

T1691 HN

NH

O

CH2OH

O O

O

NH

HN

H0990

O

O

NO2

C H

P1143

O

O

NH

N H

O

N0562

T1426 O CH2 C OH N

O

CH2OH

O

O O

O

O

O

HN O

H0983

N

N0561

H N

O

O O

M1489

C H

O

O

H1070

O

O

NH N H

O

O

O

. 6HCl

O

O

H0982 O

HN

O

O

Materials Chemistry

H1215

O

O

O

O

O

O

O

O

O

O

O

O

F0451

O

N Bn O

O

O

O

O

O

F0448

O

O

O

O O

D1668 O

O

O

O

D2321

Bn

O

O

Synthetic Organic Chemistry

O

O

O

O

O

D2684

O CH3CH2O C CH2

O CH2 C OCH2CH3 N N N

O CH2 C OCH2CH3

N O CH2 C OCH2CH3

T1600

T2642 O CH2 C OC(CH3)3

S S

S

HN

HN

NH

S

NH H N

H N

HN

NH N H

. 3HCl

N

O HO C CH2

O

N

N

CH2 C OC(CH3)3

N CH2 C OC(CH3)3 O

T2541

T1879

T1972

O CH2 C OC(CH3)3 N HN

CH3

O N

CH2 C OC(CH3)3

N

N

N

CH3

CH3

CH2 C OC(CH3)3

S

S

N S

O

Product No.

Product Name

A1603 A1604 A1404 A1552 A1323 A1324

4'-Acetylbenzo-15-crown 5-Ether 4'-Acetylbenzo-18-crown 6-Ether 4'-Aminobenzo-15-crown 5-Ether 1-Aza-12-crown 4-Ether 1-Aza-15-crown 5-Ether 1-Aza-18-crown 6-Ether

Unit Size

250mg 1g 1g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

1g 1g 1g 1g 5g 5g

343

Materials Chemistry

Synthetic Organic Chemistry

Macrocycles for Host-Guest Chemistry

Product No.

Product Name

B1249 B1154 B1539 B2245 B2189 B2181 C1713 C1714 C1942 C1943 C0858 C0859 C0860 C1736 D2743 D2744 D2323 D2877 D1533 D2878 D1830 D2684 D2321 D1668 F0448 F0451 H1070 H1215 H0932 H0982 H0983 H0990 M1489 N0561 N0562 P1143 T1874 T1875 T1426 T1691 T1597 T2540 T1959 T1876 T1878 T1600 T2642 T2541 T1879 T1972

Benzo-12-crown 4-Ether Benzo-15-crown 5-Ether Benzo-18-crown 6-Ether Bis(1,4-phenylene)-34-crown 10-Ether 4'-Bromobenzo-15-crown 5-Ether 4'-Bromobenzo-18-crown 6-Ether 4'-Carboxybenzo-15-crown 5-Ether 4'-Carboxybenzo-18-crown 6-Ether 15-Crown-4 [4-(2,4-Dinitrophenylazo)phenol] 18-Crown-5 [4-(2,4-Dinitrophenylazo)phenol] 12-Crown 4-Ether 15-Crown 5-Ether 18-Crown 6-Ether 24-Crown 8-Ether 4,10-Diaza-12-crown 4-Ether 4,10-Diaza-15-crown 5-Ether 4,13-Diaza-18-crown 6-Ether Dibenzo-15-crown 5-Ether Dibenzo-18-crown 6-Ether Dibenzo-21-crown 7-Ether Dibenzo-24-crown 8-Ether Dibenzo-30-crown 10-Ether N,N '-Dibenzyl-4,13-diaza-18-crown 6-Ether Dicyclohexano-18-crown 6-Ether 4'-Formylbenzo-15-crown 5-Ether 4'-Formylbenzo-18-crown 6-Ether 1,4,7,10,13,16-Hexaazacyclooctadecane 1,4,7,10,13,16-Hexaazacyclooctadecane Hexahydrochloride 4,7,13,16,21,24-Hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane 2-(Hydroxymethyl)-12-crown 4-Ether 2-(Hydroxymethyl)-15-crown 5-Ether 2-(Hydroxymethyl)-18-crown 6-Ether 4'-Methoxycarbonylbenzo-15-crown 5-Ether 4'-Nitrobenzo-15-crown 5-Ether 4'-Nitrobenzo-18-crown 6-Ether N-Phenylaza-15-crown 5-Ether 1,4,7,10-Tetraazacyclododecane 1,4,7,10-Tetraazacyclododecane-1,4,7,10-tetraacetic Acid 1,4,7,10-Tetraazacyclododecane Tetrahydrochloride 1,4,8,12-Tetraazacyclopentadecane 1,4,8,11-Tetraazacyclotetradecane Tetraethyl 1,4,8,11-Tetraazacyclotetradecane-1,4,8,11-tetraacetate 1,4,8,11-Tetrathiacyclotetradecane 1,5,9-Triazacyclododecane 1,4,7-Triazacyclononane 1,4,7-Triazacyclononane Trihydrochloride Tri-tert-butyl 1,4,7,10-Tetraazacyclododecane-1,4,7,10-tetraacetate Tri-tert-butyl 1,4,7,10-Tetraazacyclododecane-1,4,7-triacetate 1,4,7-Trimethyl-1,4,7-triazacyclononane (stabilized with NaHCO3) 1,4,7-Trithiacyclononane

Unit Size

B1809

1g 1g 100mg

5g

Calixarenes

5g 1g 1g 1g 100mg

1g 1g 1g 5g 200mg 1g 1g 1g 1g 200mg 1g 1g 1g 200mg 200mg

T2563

tBu

CH2 OH

4

C1455

5g 5g 5g 100mg 5g 5g 1g 1g 100mg 100mg 5mL 25mL 100g 1g 100mg 1g 5g 1g 25g 1g 5g 1g 5g 5g 1g 500mg 100mg 100mg 5g 5g 25g 1g 1g 5g 5g 5g 5g 1g 5g 5g 5g 200mg 1g 100mg 5g 5g 1g 200mg 5g 500mg

H0714

CH2

B1750

1g 1g 100mg 1g

tBu

OH

1mL 5mL 25g

1g

B2221 tBu

CH2 OH

5

H0713

6

C1435

tBu

tBu

CH2

CH2 OH

1g 1g 1g

8

CH2

4

O

OH

CH2 4

OH

CH2 6

OH

8

CH2 C OCH2CH3 O

344

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Macrocycles for Host-Guest Chemistry

H0889

S0469

S0470 SO3H

S0471

U0069 SO3H

SO3H

HO

. xH2O CH2

CH2

O C CH3

n

OH

O n = 6,8

CH2 4

OH

OH

. H 2O

CH CH3(CH2)10

8

6

. xH2O

OH

CH2

4

. xH2O

Product Name

B1809 B2221 H0714 B1750 T2563 C1455 H0713 C1435 H0889 S0469 S0470 S0471 U0069

4-tert-Butylcalix[4]arene 4-tert-Butylcalix[5]arene 4-tert-Butylcalix[6]arene (contains 5-10% Benzene) 4-tert-Butylcalix[8]arene Tetraethyl 4-tert-Butylcalix[4]arene-O,O ',O '',O '''-tetraacetate Calix[4]arene (contains ca. 8% Chloroform) Calix[6]arene Calix[8]arene 4-Methyl-1-acetoxycalixarene [mixture of [6] and [8]] (contains 5-10% Acetone) 4-Sulfocalix[4]arene Hydrate 4-Sulfocalix[6]arene Hydrate 4-Sulfocalix[8]arene Hydrate C-Undecylcalix[4]resorcinarene Monohydrate

Unit Size

B2296

1g

5g 5g 200mg 100mg 1g 1g 100mg 1g 1g 1g

B2310

Thiacalixarenes

tBu

SO2

4

O 4

OH

Bu

S

S

25g 100mg 25g 25g 1g 1g 5g 5g 1g 5g 5g 5g 1g

B2312 t

tBu

5g

Materials Chemistry

Product No.

CH2 C OCH2CH3

OH

4

O

S0477 tBu

SO2 4

OH

Product No.

Product Name

B2296 B2310 B2312 S0477

4-tert-Butylthiacalix[4]arene 4-tert-Butyl-1-(ethoxycarbonylmethoxy)thiacalix[4]arene 4-tert-Butylsulfonylcalix[4]arene 4-Sulfothiacalix[4]arene Sodium Salt

Unit Size 1g 1g 1g 1g

5g 5g 5g 5g

D4471 OCH3 CH2

Pillararenes OCH3

Product No.

Product Name

D4471

Dimethoxypillar[5]arene

5

Unit Size

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

Synthetic Organic Chemistry

CH3

100mg

345

Macrocycles for Host-Guest Chemistry

Synthetic Organic Chemistry

C1749

D2210

N +

P1165

N +

Cyclophanes

S

4PF6 + N

S

+ N

T1378 HN(CH2)4NH

H2C

CH2

Materials Chemistry

HN(CH2)4NH

Product No.

Product Name

C1749 D2210 P1165 T1378

Cyclobis(paraquat-1,4-phenylene) Tetrakis(hexafluorophosphate) 2,11-Dithia[3.3]paracyclophane [2.2]Paracyclophane 1,6,20,25-Tetraaza[6.1.6.1]paracyclophane

Unit Size

A2122

100mg 100mg 500mg 1g 100mg

A1916

A2123

α-CD

Cyclodextrins

NH2

C0776

. xH2O

NH2

(2AS, 3AS)-α-CD

B3026

γ-CD

β-CD

. xH2O C0869

C0900 C0777

H0979 OR O

CH3 RO

C

. xH2O

NH2

(2AS, 3AS)-γ-CD

(2AS, 3AS)-β-CD

RO

OR

CH3

α-CD

R = permethyl-α-CD

RO CH3

γ-CD

β-CD

R=

O

CH2CHO n = 0,1,2...

M1356

M1212

M1876

M1956

n

7

H

M1741

O SO2Mes OR O RO

O

RO

7

α-CD

RO

R = H, CH3

γ-CD

β-CD

R = permethyl-α-CD

. xH2O

OTs

M1957

M1644

M1381

M1645

P0977

OTs

OTs

OTs

OH O HO O 7 HO cross-linked by Epichlorohydrin

γ−CD α-CD

OTs

T2452

T2451

RO RO

RO

346

OR RO

N HN

RO

OR OR

T1844

T1094

T2450 CH3

OR

OR

NH N

γ-CD

β-CD

NH N N HN

OR

R = permethyl-α-CD

R = permethyl-α-CD OR

OTs

OCH3 O

OAc O AcO AcO

RO

O

CH3O 7

CH3O

O

7

C

OR

OR R = permethyl-α-CD

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Macrocycles for Host-Guest Chemistry

3A-Amino-3A-deoxy-(2AS,3AS)-α-cyclodextrin Hydrate 200mg 1g 200mg 1g 3A-Amino-3A-deoxy-(2AS,3AS)-β-cyclodextrin Hydrate 3A-Amino-3A-deoxy-(2AS,3AS)-γ-cyclodextrin Hydrate 1g 2,2-Bis[4-(per-O-methyl-α-cyclodextrin-6-yloxy)phenyl]propane 10mg α-Cyclodextrin 10g 25g 100g β-Cyclodextrin 25g 100g 500g β-Cyclodextrin 25g γ-Cyclodextrin 5g 25g 100g Hydroxypropyl-β-cyclodextrin 25g 100g 25g 250g Methyl-β-cyclodextrin (mixture of several Methylated) 1g Mono-6-O-mesitylenesulfonyl-γ-cyclodextrin Mono-6-O-(2-naphthyl)-per-O-methyl-α-cyclodextrin 10mg Mono-2-O-(p-toluenesulfonyl)-α-cyclodextrin 1g Mono-2-O-(p-toluenesulfonyl)-β-cyclodextrin Hydrate 1g Mono-2-O-(p-toluenesulfonyl)-γ-cyclodextrin 1g 200mg 1g Mono-6-O-(p-toluenesulfonyl)-α-cyclodextrin Mono-6-O-(p-toluenesulfonyl)-β-cyclodextrin 200mg Mono-6-O-(p-toluenesulfonyl)-γ-cyclodextrin 200mg Poly-β-cyclodextrin (Cross-linked by Epichlorohydrin) 1g 5,10,15,20-Tetrakis[3,5-bis(per-O-methyl-α-cyclodextrin-6-yloxy)phenyl]-21H,23H-porphine 10mg 10mg 5,10,15,20-Tetrakis[4-(per-O-methyl-α-cyclodextrin-6-yloxy)phenyl]-21H,23H-porphine Triacetyl-β-cyclodextrin 25g Trimethyl-β-cyclodextrin 1g 1,1,1-Tris[4-(per-O-methyl-α-cyclodextrin-6-yloxy)phenyl]ethane 10mg

Unit Size

Materials Chemistry

Product Name

A2122 A1916 A2123 B3026 C0776 C0900 C0777 C0869 H0979 M1356 M1212 M1876 M1956 M1741 M1957 M1644 M1381 M1645 P0977 T2452 T2451 T1844 T1094 T2450

Synthetic Organic Chemistry

Product No.

References 1) Calixarene A. Ikeda, S. Shinkai, . 1997, , 1713; M. Ayabe, S. Shinkai, 2) Cyclodextrin K. Takahashi, . 1998, , 2013. 3) Thiacalixarene 2004, number N. Morohashi, S. Miyano, , 2.

2003, number

, 2.

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

347

Materials Chemistry

Synthetic Organic Chemistry

Building Blocks for Dendrimers

Building Blocks for Dendrimers Dendrimers are a single dendritic polymer consisting of three layers, its core, dendron regularly branched from the core, and the exterior surface layer. The typical species become globular and their size is in a clear-cut nm scale, having physical properties different from conventional straight polymer. Since their report in 1984 by Tomalia and co-workers, dendrimers have received much attention in many areas.1) Nowadays, applications of dendrimers are examined in chemical sensors, catalysts, electronics, photonics and medicines.2, 3) Functional elements and functional groups can be introduced into the core, dendron and surface layer. The synthetic technique is divided mainly into the divergent method, where synthesis proceeds from the center core toward the outside, and the convergent method, where synthesis proceeds from the exterior shell to the core. For the synthesis of the regularly branched portions, multifunctional compounds have been utilized. The 1,3,5-trisubstituted benzenes, shown below are useful building blocks for dendrimers. Please refer to our website for other building blocks. We provide the structure search on the website and you can search by the substructure.

B3586

B2081

B2118

B2248

B2865

BnO

CH2OH

OCH3

BnO O

H2N

HOCH2

O

NH2

OH

CH2Br

CH2O

COOH

CH2Br

BnO

OCH3 O

O

CH3O

O

O

O

CH2OH

R

R

OCH3

OCH2

O

R

CH2O

CH3O

OCH3 CH3O

CH2O R=

OCH3

O C OCH3

R

BnO

B2052

B2246

B2247

tBu

Ph

Si O

CH3O

CH2OH

CH3O

O Si Ph

Ph

Cl

AcO

OAc

D2651 COOH

OBn

D2824

Br OH

O

NO2

BnO

AcO

Si O

H3C

CH2OH

OAc

OBn

BnO

OBn

D2832

OBn

BnO

BnO

Br

NCO

COOH

Br

Br

HO

Br

D2875 CONH2

COCH3

Cl

OBn

D2353

D1981

Cl

CHO

CHO

I0302

Br

D3184 COCH3

CH2Br

TMS

Br

D2085

B2093

D2724

Br

O

COOH

CH2OH

COCH3

348

D2844 COCH3

D2267

BnO

O2N

CH3O

D1978

OCH3

H3C C

CH2Br

CH3O

CH2OH

H 3C

CH2O

CH3O

CH3O

COOH

CH3O

CH2O

Ph

C1258

B2866

CH2O

CH2O

tBu

B2120

CH3O

CH3O

CH2OH

OH

HO

OH

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Building Blocks for Dendrimers

D2656 COOH

HO

D1484

D1534

HO

CH3O

OH

D2609 COOH

OCH3

CH3O

D2657 CH2OH

OCH3

H0794

CH3O

OCH3

CH3O

CH2COOH

OCH3

B2051

M1929

COOH

D2215

Br

T2719

OH

D1737

HO

Ph

Si O

CH3O

OH

COOCH3

tBu

O Si Ph Ph

D2655

OCH3

BnO

OBn

T2760 COOCH2CCl3

HO

OCH3

B2092

Ph

COOCH3

COOCH3

COOCH3

Br

CH3O

CH3O

COOCH3

OH

OCH3

D2950

tBu

HO

CH3O

CH2Br

M1413 COOH

OCH3

Materials Chemistry

H1412

CH3O

CONH2

CH3O

OCH3

D2594 COCl

D1558 CHO

NH2

CH2OH

OH

D1164

Synthetic Organic Chemistry

D0570 D2554

OH

C CH

HC C

C CH

T2647 COOH

CH2Br

BrCH2

CH2Br HOOC

COOH

Product No.

Product Name

B3586 B2081 B2118 B2248 B2865 B2052 B2246 B2247 B2120 B2866 C1258 D1978 D2844 D2085 D3184 D2267 D2651 B2093 D2832 D2353 D2824 D2724 I0302 D1981

1,3,5-Benzenetrimethanol 3,5-Bis(4-aminophenoxy)benzoic Acid 3,5-Bis[3,5-bis(benzyloxy)benzyloxy]benzyl Bromide 3,5-Bis[3,5-bis(3,5-dimethoxybenzyloxy)benzyloxy]benzyl Bromide 3,5-Bis[3,5-bis(methoxycarbonyl)phenoxymethyl]phenol 3,5-Bis(tert-butyldiphenylsilyloxy)benzyl Alcohol 3,5-Bis(3,5-dimethoxybenzyloxy)benzyl Alcohol 3,5-Bis(3,5-dimethoxybenzyloxy)benzyl Bromide 3,5-Bis(4-nitrophenoxy)benzoic Acid 5-(tert-Butyldiphenylsilyloxy)-1,3-benzenedimethanol 1-Chloro-3,5-dimethoxybenzene 3',5'-Diacetoxyacetophenone 3,5-Diacetoxybenzoic Acid 3',5'-Dibenzyloxyacetophenone 3,5-Dibenzyloxybenzaldehyde 3,5-Dibenzyloxybenzoic Acid 3,5-Dibenzyloxybenzyl Alcohol 3,5-Dibenzyloxybenzyl Bromide 3,5-Dibromobenzaldehyde 3,5-Dibromobenzoic Acid 3',5'-Dibromo-4'-hydroxyacetophenone 3,5-Dibromo-1-trimethylsilylbenzene 3,5-Dichlorophenyl Isocyanate 3',5'-Dihydroxyacetophenone

Unit Size 1g 1g 1g

1g 1g 1g 10g 10g 1g 1g 5g 5g 5g 5g 5g 5g 10g

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

5g 5g 5g 1g 200mg 1g 5g 5g 5g 5g 25g 25g 5g 10g 5g 25g 25g 25g 25g 10g 25g 25g 10g 25g

349

Materials Chemistry

Synthetic Organic Chemistry

Building Blocks for Dendrimers

Product No.

Product Name

D2875 D0570 D2554 D2656 D1484 D1164 D1558 D1534 D2609 D2594 D2657 D2950 H1412 H0794 M1413 B2051 B2092 M1929 D2215 D1737 D2655 T2760 T2719 T2647

3,5-Dihydroxybenzamide 3,5-Dihydroxybenzoic Acid 3,5-Dihydroxybenzoic Acid 3,5-Dihydroxybenzyl Alcohol 3,5-Dimethoxyaniline 3,5-Dimethoxybenzaldehyde 3,5-Dimethoxybenzamide 3,5-Dimethoxybenzoic Acid 3,5-Dimethoxybenzoyl Chloride 3,5-Dimethoxybenzyl Alcohol 3,5-Dimethoxybenzyl Bromide 3,5-Dimethoxyphenylacetic Acid Hexaphenylbenzene 5-Hydroxyisophthalic Acid 5-Methoxyresorcinol Methyl 3,5-Bis(tert-butyldiphenylsilyloxy)benzoate (ca. 20% in Toluene, ca. 0.28mol/L) Methyl 3,5-Dibenzyloxybenzoate Methyl 3,5-Dibromobenzoate Methyl 3,5-Dihydroxybenzoate Methyl 3,5-Dimethoxybenzoate 2,2,2-Trichloroethyl 3,5-Dihydroxybenzoate (ca. 20% in Dichloromethane, ca. 1mol/L) 1,3,5-Triethynylbenzene 1,3,5-Tris(bromomethyl)benzene 1,3,5-Tris(4-carboxyphenyl)benzene

Unit Size 25g 25g 5g 5g 5g 25g 5g 5g 5g 1g 1g 25g

5g 5g 25g 5g 1g 1g 1g

5g 500g 500g 25g 25g 25g 5g 500g 25g 25g 25g 5g 5g 500g 1g 25g 25g 25g 250g 25g 25g 5g 5g 5g

References 1) D. A. Tomalia, J. R. Dewald, M. R. Hall, S. J. Martin, P. B. Smith, Preprints of the 1st SPSJ International Polymer Conference, Society of Polymer Science Japan, Kyoto, 1984, p 65; D. A. Tomalia, J. M. J. Fréchet, 2002, , 2719. 2) F. Vögtle, G. Richardt, N. Werner, in , Wiley-VCH, Weinheim, 2009. 2010, 3) D. Astruc, E. Boisselier, C. Ornelas, , 1857.

350

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Derivatizing Reagents for Solubility Improvement

Alkyl groups do not affect molecular electronic properties, because they do not strongly interact with π-conjugates. However, the effect of alkyl groups is large in the molecule-assembled solid state, modifying solubility and melting point when alkyl groups are introduced. In particular, organic devices require alkyl derivatizations to increase solubility, because solution-processible printing technologies are required for large scale manufacturing. In addition, introduction of a long alkyl chain to an organic molecule produces a liquid crystal material.

CH3

C5 Alkyl Groups

P0055

CH3

P1177

OH

B0628

CH3

NH2

U0081

CH3

Product Name Amylamine 1-Bromopentane 1-Pentanethiol 1-Pentanol Pentylmagnesium Bromide (18% in Tetrahydrofuran, ca. 1mol/L) Undecafluoropentyl Iodide Valeric Acid

CH3

SH

OH

Unit Size

B0600

25mL 100mL 25mL 25mL 25mL

500mL 500mL 500mL 500mL 250g 5g 25g 25mL 500mL

H0105

H0130

O

C6 Alkyl Groups

CH3

H0842

NH2

Br

O CF3(CF2)4I

MgBr

A0445 B0628 P0053 P0055 P1177 U0081 V0003

CH3

CH3

V0003

Product No.

H0134

P0053

Materials Chemistry

A0445

CH3

Br

H0821

Li

CH3

CH3

OH

H0103

MgBr

CH3

CH3

OH

T2479

SH

CF3(CF2)5Br

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

Synthetic Organic Chemistry

Derivatizing Reagents for Solubility Improvement

351

Derivatizing Reagents for Solubility Improvement

Synthetic Organic Chemistry

T1098

Materials Chemistry

CF3(CF2)5I

Product No.

Product Name

B0600 H0105 H0130 H0134 H0842 H0821 H0103 T2479 T1098

1-Bromohexane Hexanoic Acid 1-Hexanol Hexylamine Hexyllithium (30% in Hexane, ca. 2.3mol/L) Hexylmagnesium Bromide (20% in Tetrahydrofuran, ca. 1mol/L) Hexyl Mercaptan Tridecafluorohexyl Bromide Tridecafluorohexyl Iodide

Unit Size

B0598

H0033

CH3

H0045

OH

H0029

CH3

C7 Alkyl Groups

CH3

Br

H0822

NH2

25g 500g 25mL 500mL 25mL 500mL 25mL 100mL 500mL 100mL 250g 25mL 500mL 5g 25g 5g 25g

H0030

O

CH3

SH

P1753

CH3

Product Name

B0598 H0029 H0030 H0033 H0045 H0822 P1753 P1839

1-Bromoheptane 1-Heptanethiol Heptanoic Acid 1-Heptanol Heptylamine Heptylmagnesium Bromide (21% in Tetrahydrofuran, ca. 1mol/L) Pentadecafluoroheptyl Bromide Pentadecafluoroheptyl Iodide (stabilized with Na2S2O3)

P1839

CF3(CF2)6I

Unit Size

B0596

25g 500g 10g 25g 25mL 500mL 25mL 500mL 25mL 500mL 250g 5g 5g 25g

B0626

D1800

CH3

C8 Alkyl Groups

352

OH

CF3(CF2)6Br

MgBr

Product No.

CH3

CH3

CH3 Br

CH3

Br

CH3

CH3 NH2

Chemicals itemized in this TCI Reagent Guide are for testing or research purpose only. Therefore, please note those chemicals are not guaranteed in the user's favor relating to various problems under the Patent Law that might occur through their use.

Derivatizing Reagents for Solubility Improvement

E1031

E0120

E0122

E0126

E0127

SH

CH3

CH3

OH

H0946

NH2

. HCl

OH

P1084

O0025

CF3(CF2)7I

O0027

CH3

OH CH3

SH

CH3

OH

O0240

NH2 CH3

MgBr

Product No.

Product Name

B0596 B0626 D1800 E1031 E0120 E0122 E0126 E0127 E0128 H0946 P1084 O0025 O0027 O0036 O0045 O0240

1-Bromo-2-ethylhexane 1-Bromooctane 1,5-Dimethylhexylamine 2-Ethyl-1-hexanethiol 2-Ethylhexanoic Acid 2-Ethyl-1-hexanol 2-Ethylhexylamine 2-Ethylhexylamine Hydrobromide 2-Ethylhexylamine Hydrochloride Heptadecafluoro-n-octyl Bromide Heptadecafluoro-n-octyl Iodide 1-Octanethiol n-Octanoic Acid 1-Octanol n-Octylamine n-Octylmagnesium Bromide (ca. 22% in Tetrahydrofuran, ca. 1mol/L)

Unit Size

B0933

CH3

C9 Alkyl Groups

CH3

CH3

O

CF3(CF2)7Br

O0045

N0292

NH2 . HBr

CH3

Materials Chemistry

CH3

NH2 CH3

CH3

O0036

CH3

CH3

CH3

E0128

CH3

CH3

Synthetic Organic Chemistry

O CH3

25mL 100mL 500mL 25mL 500mL 25mL 25g 100g 25mL 500mL 25mL 500mL 25mL 100mL 500mL 25g 25g 5g 25g 25g 25mL 500mL 25mL 500mL 25mL 500mL 25mL 500mL 250g

N0808

Br

N0288 P0952

CF3(CF2)8Br

O CH3

OH

N0297

OH

CH3

NH2

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

353

Materials Chemistry

Synthetic Organic Chemistry

Derivatizing Reagents for Solubility Improvement

Product No.

Product Name

B0933 N0808 N0288 P0952 N0292 N0297

1-Bromononane Nonadecafluorononyl Bromide Nonanoic Acid Nonanoic Acid 1-Nonanol Nonylamine

Unit Size 25mL 500mL 5g 25mL 500mL 25mL 500mL 25mL 500mL 25mL D0033

B4401

CH3

C10 Alkyl Groups

D0016

B0583

NH2

CH3

D0017

D0031

CH3

Br

D1442

CH3 Br

CH3

H0844 CH3

O SH

CH3

CH3

OH

CH3

OH CH3

Product No.

Product Name

D0033 B0583 B4401 D0016 D0017 D0031 D1442 H0844

1-Aminodecane 1-Bromodecane 1-Bromo-3,7-dimethyloctane 1-Decanethiol Decanoic Acid 1-Decanol 3,7-Dimethyl-1-octanol Heneicosafluorodecyl Iodide

Unit Size

C11 Alkyl Groups

354

B0934

CH3

U0005

O CH3

CH3

25mL 100mL 25mL 5g 25mL 25g 25mL 25mL

A0761

U0004

CF3(CF2)9I

OH

NH2

CH3

500mL 500mL 25g 500mL 400g 500mL 500mL 5g

U0066

Br

CH3

SH

U0040

OH

CH3

OH

OH

Product No.

Product Name

A0761 B0934 U0066 U0004 U0005 U0040

1-Aminoundecane 1-Bromoundecane 1-Undecanethiol Undecanoic Acid 1-Undecanol 6-Undecanol

CH3

CH3

Unit Size

Availability or specification of the listed products are subject to change without prior notice.

10mL 25mL 500mL 5mL 25g 250g 25mL 500mL 5g

Derivatizing Reagents for Solubility Improvement

B0587

D0980

CH3(CH2)11Br

D1452

CH3(CH2)11NH2

CH3(CH2)11NH2

CH3

OH

CH3(CH2)11SH

CH3

L0011

. HCl

Product Name

B0587 B3457 D0970 D0980 D1452 L0011

1-Bromododecane 2-Butyl-1-n-octanol 1-Dodecanethiol Dodecylamine Dodecylamine Hydrochloride Lauric Acid

O CH3(CH2)10

C OH

Materials Chemistry

Product No.

Unit Size 25mL 500mL 25mL 500mL 25mL 500mL 25g 400g 25g 500g 25g 500g

A0762

C13 Alkyl Groups

D0970

Synthetic Organic Chemistry

C12 Alkyl Groups

B3457

B0935

CH3(CH2)12NH2

T0412

CH3(CH2)12Br

O CH3(CH2)11 C OH

T0803

CH3(CH2)12OH

Product No.

Product Name

A0762 B0935 T0412 T0803

1-Aminotridecane 1-Bromotridecane Tridecanoic Acid 1-Tridecanol

Unit Size 10g 5mL 25g

B0233

C14 Alkyl Groups

M0476

CH3(CH2)13Br

25g 25mL 500g 25g

T0082

O CH3(CH2)12 C OH

CH3(CH2)13SH

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

355

Derivatizing Reagents for Solubility Improvement

Synthetic Organic Chemistry

T0084

T0090

CH3(CH2)13OH

CH3(CH2)13NH2

Product No.

Product Name

B0233 M0476 T0082 T0084 T0090

1-Bromotetradecane Myristic Acid 1-Tetradecanethiol 1-Tetradecanol Tetradecylamine

Unit Size 25mL 500mL 25g 500g 25mL 25mL 500mL 25g 400g

Materials Chemistry

A0763

C15 Alkyl Groups

P0035

CH3(CH2)14NH2

P0036

O

CH3(CH2)14MgBr

Product Name

A0763 B0936 P0836 P0035 P0036 P1251

1-Aminopentadecane 1-Bromopentadecane 1-Pentadecanethiol Pentadecanoic Acid 1-Pentadecanol Pentadecylmagnesium Bromide (ca. 15% in Tetrahydrofuran, ca. 0.4mol/L)

Unit Size

B0599

C16 Alkyl Groups

356

Br CH3

P1145 P0002

CH3

OH CH3

10g 25mL 250mL 10mL 100g 500g 100g 500g 250g

H0068

CH3

H1461

CH3(CH2)15NH2

25g 25g

B4544

CH3(CH2)15Br

H0074

CH3(CH2)15OH

CH3(CH2)14SH

CH3(CH2)14Br

Product No.

H0071

P0836

P1251

CH3(CH2)14OH

CH3(CH2)13 C OH

B0936

O CH3(CH2)14 C OH

Availability or specification of the listed products are subject to change without prior notice.

CH3(CH2)15SH

Derivatizing Reagents for Solubility Improvement

Product Name

B0599 B4544 H0068 H0071 H0074 H1461 P1145 P0002

1-Bromohexadecane 7-(Bromomethyl)pentadecane 1-Hexadecanethiol 1-Hexadecanol Hexadecylamine 2-Hexyl-1-decanol Palmitic Acid Palmitic Acid

Unit Size 25g 500g 5mL 25mL 25mL 500mL 25g 500g 25g 500g 25mL 500mL 5g 25g 500g

H0019

B0937

CH3(CH2)16NH2

H0018

O

Product No.

Product Name

A0764 B0937 B1456 H0019 H0018 H1401

1-Aminoheptadecane 1-Bromoheptadecane 1-Bromo-2-methylhexadecane Heptadecanoic Acid 1-Heptadecanol 9-Heptadecanol

CH

(CH2)7CH3

5g 25g

O0005

CH3(CH2)17Br

S0163

. HCl

CH CH2Br

Unit Size

C18 Alkyl Groups

CH3(CH2)17NH2

CH3 CH3(CH2)13

OH CH3(CH2)7

B0625

O0099

CH3(CH2)16Br

H1401

CH3(CH2)16OH

CH3(CH2)15 C OH

B1456

Materials Chemistry

A0764

C17 Alkyl Groups

Synthetic Organic Chemistry

Product No.

100g 5g

10g 25g 1g 500g 25g 1g

O0006

CH3(CH2)17SH

CH3(CH2)17OH

O0014

O CH3(CH2)16 C OH

CH3(CH2)17NH2

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

357

Synthetic Organic Chemistry

Derivatizing Reagents for Solubility Improvement

Product No.

Product Name

B0625 O0005 O0006 O0099 S0163 O0014

1-Bromooctadecane 1-Octadecanethiol 1-Octadecanol Octadecylamine Hydrochloride Stearic Acid Stearylamine

Unit Size 25g 25g 25g 25g 25g D2704

D2712 Cl

Dialkyldichlorosilanes

CH3(CH2)3

Si (CH2)3CH3

Materials Chemistry

Cl

D4336 Cl

CH3(CH2)5

500g 400g 500g 25g 500g 500g

Si (CH2)5CH3 Cl

Cl CH3(CH2)7 Si

(CH2)7CH3

Cl

D2710 Cl CH3(CH2)4 Si (CH2)4CH3 Cl

358

Product No.

Product Name

D2704 D2712 D4336 D2710

Dibutyldichlorosilane Dichlorodihexylsilane Dichlorodi-n-octylsilane Dichlorodipentylsilane

Unit Size

Availability or specification of the listed products are subject to change without prior notice.

5g 5g

25g 25g 1g 5g

Synthetic Organic Chemistry Materials Chemistry

This TCI Reagent Guide is not an all inclusive guide of all the products available from us. Please refer to our catalog for further information or visit our web site.

359

Abbreviations Descriptors ompnprim sec tert αβγδεημ-

ortho meta para normal primary secondary tertiary alpha beta gamma delta epsilon eta mu

τωBNOPScis trans (Z )(E )threo erythro D-

tau(tele) omega boron position nitrogen position oxygen position phosphorus position sulfur position cis form trans form Z(zusammen)form E(entgegen)form threo form erythro form D form

LDL-

d - or (+)l - or (−)dl - or (±)(R )(S )meso syn anti asym s- or sym active leuco -

L form DL form dextro rotation levo rotation racemic mixture R(rectus)form S(sinister)form meso form syn form anti form asymmetric form symmetric form active form leuco form

Products / Ligands acac ADDP AIBN BINAP BINOL bipy BMS bpy BSA CD CDI cod cot CSA CSI DABCO DAST dba DBAD DBN DBU DCC DDQ DEAD DET DHP DIAD DIBAL DIBAL-H DIEA DIPEA DIPT DMA DMAP DME DMF dmit DMP DMPU DMS DMSO DMTSF DOXYL DPPA

360

Acetylacetone 1,1'-(Azodicarbonyl)dipiperidine 2,2'-Azobis(isobutyronitrile) 2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl Binaphthol = bpy Borane - Dimethyl Sulfide Complex Bipyridine N ,O -Bis(trimethylsilyl)acetamide Cyclodextrin N ,N '-Carbonyldiimidazole Cyclooctadiene Cyclooctatetraene Camphorsulfonic Acid Chlorosulfonyl Isocyanate 1,4-Diazabicyclo[2.2.2]octane (Diethylamino)sulfur Trifluoride Dibenzylideneacetone Di-tert -butyl Azodicarboxylate 1,5-Diazabicyclo[4.3.0]non-5-ene 1,8-Diazabicyclo[5.4.0]-7-undecene N ,N '-Dicyclohexylcarbodiimide 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone Diethyl Azodicarboxylate Diethyl Tartrate 3,4-Dihydro-2H -pyran Diisopropyl Azodicarboxylate = DIBAL-H Diisobutylaluminum Hydride = DIPEA N ,N -Diisopropylethylamine Diisopropyl Tartrate N ,N -Dimethylacetamide 4-Dimethylaminopyridine 1,2-Dimethoxyethane N ,N -Dimethylformamide 4,5-Dimercapto-1,3-dithiole-2-thione Dess-Martin Periodinane N ,N '-Dimethylpropyleneurea Dimethyl Sulfide Dimethyl Sulfoxide Dimethyl(methylthio)sulfonium Tetrafluoroborate 4,4-Dimethyloxazolidine-1-oxyl Diphenylphosphoryl Azide

dppf DTBP DVB EDAC EDC EDC EDCI EDTA FAMSO Fc HMDS HMPA HMPT HOAt HOBt HOSu IBX Im Imid LAH LDA LHMDS LiHMDS LTA MCPBA MEK MTBE MVK NaHDMS nbd NBS NCS NHC NIS NMO NMP Norphos Pc PCC PDC PEG PG phen

1,1'-Bis(diphenylphosphinoferrocene) Di-tert -butyl Peroxide Divinylbenzene = EDCl 3-(3-Dimethylaminopropyl)-1-ethylcarbodiimide = EDCl 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Ethylenediaminetetraacetic Acid Formaldehyde Dimethyl Dithioacetal S -Oxide Ferrocene 1,1,1,3,3,3-Hexamethyldisilazane Hexamethylphosphoric Triamide Hexamethylphosphorous Triamide 1-Hydroxy-7-azabenzotriazole 1-Hydroxybenzotriazole N -Hydroxysuccinimide 2-Iodoxybenzoic Acid Imidazole = Im Lithium Aluminum Hydride Lithium Diisopropylamide = LiHMDS Lithium Hexamethyldisilazide Lead Tetraacetate m -Chloroperoxybenzoic Acid Methyl Ethyl Ketone Methyl tert -Butyl Ether Methyl Vinyl Ketone Sodium Hexamethyldisilazide 2,5-Norbornadiene N -Bromosuccinimide N -Chlorosuccinimide N -Heterocyclic Carbene N -Iodosuccinimide 4-Methylmorpholine N -Oxide N -Methyl-2-pyrrolidone 2,3-Bis(diphenylphosphino)bicyclo[2.2.1] hept-5-ene Phthalocyanine Pyridinium Chlorochromate Pyridinium Dichromate Polyethylene Glycol Prostaglandin Phenanthroline

PPTS PTSA py Salen SDS TBAB TBAD TBAF TBHP TCNQ TEMPO

Pyridinium p -Toluenesulfonate p -Toluenesulfonic Acid Pyridine N ,N '-Bis(salicylidene)ethylenediamine Sodium Dodecyl Sulfate Tetrabutylammonium Bromide = DBAD Tetrabutylammonium Fluoride tert -Butyl Hydroperoxide 7,7,8,8-Tetracyanoquinodimethane 2,2,6,6,-Tetramethylpiperidine 1-Oxyl

TFA TFAA THF THP TMTSF TNBS TPAP TPD TPDS TPP TTF

Trifluoroacetic Acid Trifluoroacetic Anhydride Tetrahydrofuran Tetrahydropyran Tetramethyltetraselenafluvalene 2,4,6-Trinitrobenzenesulfonic Acid Tetrapropylammonium Perruthenate N ,N '-Diphenyl-N ,N '-di(m -tolyl)benzidine Tetraphenyldisilane Tetraphenylporphyrin Tetrathiafulvalene

AcetylAllyloxycarbonylArylBenzyltert-ButoxycarbonylBenzyloxycarbonyl= TBDPS BenzoylCarbobenzoxy- (=Benzyloxycarbonyl-) = Cy CyclopentadienylCyclohexyl4,4'-Dimethoxytrityl2,4-Dinitrophenyl(9H-Fluoren-9-ylmethoxy)carbonyl(2-Methoxyethoxy)methyl2,4,6-Trimethylphenyl- (=Mesityl-) 4-MonomethoxytritylMethoxymethyl-

Ms Naph Np Nps Ns Piv PMB SEM TBDMS TBDPS TES Tf TIPS TMS Tol Tr Ts Z

Methanesulfonyl= Np Naphthyl2-NitrophenylsulfenylNitrobenzenesulfonyl Pivaloylp-Methoxybenzyl 2-(Trimethylsilyl)ethoxymethyltert-Butyldimethylsilyl- (=TBS) tert -ButyldiphenylsilylTriethylsilylTrifluoromethanesulfonylTriisopropylsilylTrimethylsilylp -TolylTriphenylmethyl- (=Trityl-) p-Toluenesulfonyl- (=Tosyl) =Cbz

3,5-Di-tert-butyl-4-hydroxytoluene Hydroquinone Hydroquinone Monomethyl Ether (=4-Methoxyphenol)

ONP TBC TBBP

o-Nitrophenol 4-tert-Butylcatechol 3,3',5,5'-Tetra-tert-butyl-4,4'- dihydroxybiphenyl

Protecting Groups / Functional Groups Ac Alloc Ar Bn Boc BOM BPS Bz Cbz Chx Cp Cy DMTr Dnp Fmoc MEM Mes MMTr MOM

Stabilizers BHT HQ MEHQ

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Pressure-Temperature Nomograph



How to calculate the bp under atmospheric pressure from bp under reduced pressure Connect a degree on the line C and its corresponding bp on the line A under reduced pressure using a straight line. ② An intersection found by step ① on the line B serves as an approximate bp in atmospheric pressure. ①

*This nomograph applies to nonassociated solvent. Since the bp obtained from this nomograph is an approximate value, it is not an exact bp. Reference:Science of Petroleum, Vol.II. p.1281 (1938).

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The physical properties of the typical organic solvents 1) Organic Solvents Methanol (MeOH) Ethanol (EtOH) Propanol (n -PrOH) Isopropyl Alcohol (i -PrOH) Butanol (BuOH) Isobutyl Alcohol (i -BuOH) sec -Butyl Alcohol (s -BuOH) tert -Butyl Alcohol (t -BuOH) Ethylene Glycol 1,2-Dimethoxyethane (Glyme) Diethyl Ether (Et2O) Diisopropyl Ether (i -Pr2O) Acetic Acid (AcOH) Ethyl Acetate (AcOEt) Acetic Anhydride (Ac2O) Tetrahydrofuran (THF) 1,4-Dioxane Acetone Ethyl Methyl Ketone Carbon Tetrachloride (CCl4) Chloroform (CHCl3) Dichloromethane (CH2Cl2) 1,2-Dichloroethane (ClCH2CH2Cl) Benzene (C6H6) Toluene o -Xylene Cyclohexane Pentane Hexane Heptane Acetonitrile (CH3CN) Nitromethane (CH3NO2) Dimethylformamide (DMF) Hexamethylphosphoric Triamide (HMPA) Triethylamine (Et3N) Pyridine (Py) Dimethyl Slufoxide (DMSO) Carbon Disulfide (