EXPERIMENTS IN ORGANIC CHEMISTRY From Microscale to Macroseale
Jonathan S. Nimitz University of New Mexico
WM PRENTICE HALL, Englewood Cliffs, New J...
EXPERIMENTS IN ORGANIC CHEMISTRY From Microscale to Macroseale
Jonathan S. Nimitz University of New Mexico
WM PRENTICE HALL, Englewood Cliffs, New Jersey 07632
PREFACE LABORATORY ESSENTIALS
xiii The First Steps Safety Practices in the Organic Laboratory 4 First Aid 7 Guidelines for Notebooks 8 Note on Calculating Theoretical Yields 10 Typical Organic Chemistry Desk Equipment 12 General Hints on Using Glassware and Equipment
1
12
SECTION 1
Recrystallization and Melting Points Experiment 1.1: Recrystallization of Benzoic Acid from Water 29 Experiment 1.2: Recrystallization of Naphthalene from Methanol Using Decolorizing Charcoal 30 Experiment 1.3: Choosing a Recrystallization Solvent 31
22
SECTION 2
Distillation Application: Fractional Distillation of Petroleum 40 Experiment 2.1: Fractional Distillation of an Acetone-Toluene Mixture 42
34
SECTION 3
Acid-Base Extraction Application: History, Cultivation, and Composition of Tea 53 Experiment 3.1: Separation of Benzoic Acid, m-Nitroaniline, and Naphthalene 59 Experiment 3.2: Extraction of Caffeine from Tea Leaves 61
45
SECTION 4
Thin-Layer Chromatography Application: Forensic Chemistry 65 Experiment 4.1: Determining Rf Values and Unknowns by TLC 68
Isolation of Chlorophyll and ß-Carotene from Spinach by Gradient Elution 80
Acid-Cataiyzed Dehydration of Alcohols Experiment 6.1: Cyclohexene from Cyclohexanol Experiment 6.2: Pentenes from 2-Pentanol 86
82 85
Hydration of Alkenes and Alkynes Experiment 7.1: Hydration of 2-Methyl-3-butyn-2-ol Stereochemistry: Adding Bromine to Alkenes Experiment 8.1: Addition of Bromine to Cinnamic Acid
88 93 95 98
Alkyne Formation from Vicinal Dihalides Application: Alkynes and Birth Control 103 Experiment 9.1: Phenylpropynoic Acid by Double Dehydrobromination of Cinnamic Acid Dibromide 104 Experiment 9.2: Microscale Preparation of Diphenylacetylene from Stilbene Dibromide 105
102
SN2 Reactions Experiment 10.1:
107
SECTION 11
SN1 Reactions and Kinetics Experiment 11.1: Conversion of f-Amyl Alcohol to f-Amyl Chloride Using HCl 123 Experiment 11.2: Kinetic Study of the Hydrolysis of f-Butyl Chloride 124
120
SECTION 12
Radical Halogenation and Gas Chromatography Application: Gas Chromatography and Environmental Protection 131 Experiment 12.1: Chlorination of 1-Chlorobutane 135 Experiment 12.2: Bromination of m-Toluic Acid Using NBS
126
SECTION 10
Conversion of 1 -Butanol to 1 -Bromobutane 112 Experiment 10.2: Displacement of Bromide by lodide: Preparation of 1-lodohexane by the Finkelstein Reaction 115 Experiment 10.3: Conversion of Isobutyl Alcohol to Isobutyl Bromide Using PBr3 116 Experiment 10.4: Conversion of 1-Pentanol to 1-lodopentane Using Phosphorus and lodine 116 Mechanisms Review: 117
137
Contents
VÜ
SECTION 13
Infrared Spectroscopy Experiment 13.1: Unknown Determination by IR Spectroscopy 147
138
SECTION 14
Structure Determination Practice (No experiment)
150
SECTION 15
Diels-Alder Reactions and Insecticides Experiment 15.1: Cycloaddition of Cyclopentadiene and Maleic Anhydride 187
179
SECTION 16
Catalytic Hydrogenation Application: Catalytic Hydrogenation of Vegetable Oil 191 Experiment 16.1: Hydrogenation of C/'s-5-Norbornene-Eno'o-2,3Dicarboxylic Acid Using Pt/H2 194
189
SECTION 17
Isolation of Natural Flavors and Fragrances Application: Commercial Distiliation of Essential Oils 200 Application: Vanilla Flavor from Wood 204 Experiment 17.1: Steam Distiliation of Eugenol from Cloves Experiment 17.2: Steam Distiliation of Orange Oil 207
196
206
SECTION 18
Electrophilic Aromatic Substitution Experiment 18.1 Nitration of Methyl Benzoate 214 Experiment 18.2 Dinitration of Benzoic Acid 215 Experiment 18.3 Microscale Bromination of Resorcylic Acid 216 Experiment 18.4: Microscale Friedel-Crafts Alkylation of p-Dimethoxybenzene 216
208
SECTION 19
Oxidation of a Side Chain on an Aromatic Ring Experiment 19.1: Oxidation of o-Chlorotoluene to o-Chlorobenzoic Acid Using KMn0 4 221 Experiment 19.2: Oxidation of p-Nitrotoluene to p-Nitrobenzoic Acid Using Na 2 Cr 2 0 7 /H 2 S0 4 222 Experiment 19.3: Oxidation of 2-Methylpyridine to 2Pyridinecarboxylic Acid Using KMn0 4 223
Williamson Synthesis of Ethyl Phenyl Ether Using Phase-Transfer Catalysis 228 Williamson Synthesis of p-Ethoxynitrobenzene 230 Conversion of Acetaminophen into Phenacetin 230
Experiment 20.4:
Microscale Preparation of Trityl Ethyl Ether 231
SECTION 21
Epoxidation of Afkenes Application: Epoxy Glue 234 Experiment 21.1: Preparation of Stilbene Oxide Using MCPBA 236
233
SECTION 22
Carbenes Experiment 22.1:
237
Experiment 22.2:
Addition of Dichlorocarbene to Cyclohexene 242 Microscale Addition of Dibromocarbene to 1,1Diphenylethylene 244
SECTION 23
Carbocation Rearrangements Experiment 23.1 The Pinacol Rearrangement 251 Experiment 23.2 Rearrangement of Benzopinacol 252 Experiment 23.3 Three-Step Synthesis of Camphor from Camphene 252
246
SECTION 24
Hydride Reductions Experiment 24.1: Reduction of Cyclohexanone to Cyclohexanol Using NaBH4 260 261 Experiment 24.2: Reduction of Vanillin Using NaBH4 Stereochemistry of the Reduction of 4-fExperiment 24.3: Butylcyclohexanone 262
255
SECTION 25
Oxidation of Alcohols and Aldehydes Experiment 25.1: Jones Oxidation of 2-Methylcyclohexanol 266 Experiment 25.2: Oxidation of Furfural to Furoic Acid Using K 2 Cr 2 0 7 /H 2 S0 4 267 Experiment 25.3: Oxidation of Heptanal to Heptanoic Acid Using KMn0 4 268
263
SECTION 26
Reactions of Aldehydes and Ketones with Amines Experiment 26.1: Microscale Synthesis of Benzophenone Oxime 273
270
SECTION 27
The Beckmann Rearrangement Experiment 27.1: Microscale Conversion of Cyclohexanone Oxime to Caprolactam 276
274
Contents
IX
SECTION 28
Malonic and Acetoacetic Ester Synthesis Experiment 28.1: Malonic Ester Synthesis of Cyclobutanecarboxylic Acid 281 Experiment 28.2: Acetoacetic Ester Synthesis of 2-Heptanone 284
277
SECTION 29
Alkylation and Acylation of Carbonyl Compounds Experiment 29.1: Acylation of Cyclohexanone Using the Morpholine Enamine 289
286
SECTION 30
The Wittig Reaction Experiment 30.1: Wittig Synthesis of Trans-Stilbene
291 293
SECTION 31
Reactions and Spectroscopy of Aldehydes and Ketones Experiment 31.1: Identification of an Unknown Aldehyde or Ketone 301
295
SECTION 32
Qualitative Organic Analysis Experiment 32.1: Identification of an Unknown Organic Compound 317
311
SECTION 33
Grignard Reactions and MultiStep Syntheses Experiment 33.1: Synthesis of Triphenylmethanol by Reaction of Methyl Benzoate and Phenylmagnesium Bromide 335
330
SECTION 34
Organolithium Compounds Experiment 34.1: Synthesis of Fluorene-9-Carboxylic Acid
340
SECTION 35
342
Hydrolysis of Nitriles to Carboxylic Acids Experiment 35.1: Hydrolysis of Benzonitrile to Benzoic Acid
344 346
SECTION 36
Base-Catalyzed Hydrolysis of Esters: Soap Making Experiment 36.1: Soap from Shortening 350
347
SECTION 37
Ester Synthesis Application: The Painful History of Analgesics, Antipyretics, and Anti-Inflammatory Agents 358 Experiment 37.1: Synthesis of Banana Fragrance (Isoamyl Acetate) 360 Experiment 37.2: Ethyl Acetate from Ethanol and Acetic Acid 361
Synthesis of Aspirin by Acetylation of Salicylic Acid 362 Acetylation of Furfuryl Alcohol 363 Microscale Acetylation of Benzoin with Acetic Anhydride 363 Preparation of f-Butyl Acetate from f-Butyl Alcohol and Acetyl Chloride 364
SECTION 38
Amide Synthesis Application: Mosquito Repellents 368 Experiment 38.1: Acetanilide from Aniline and Acetic Anhydride 370 Experiment 38.2: Acetylation of Glycine with Acetic Anhydride 371 Experiment 38.3: Synthesis of the Insect Repellent N,N-Diethyl-mToluamide 371 Experiment 38.4: Microscale Sulfonamide Formation by Reaction of p-Toluenesulfonyl Chloride and Methylamine 373
365
SECTION 39
Aldol Condensations Experiment 39.1: Microscale Aldol Condensation of Acetone and Benzaldehyde 382 Experiment 39.2: Condensation of Benzaldehyde and Nitromethane to form Nitrostyrene 383 Experiment 39.3: Microscale Condensation of a Nitrile and an Aromatic Aldehyde: Preparation of a-(4-Nitrophenyl) Cinnamonitrile 384 Experiment 39.4: Claisen Condensation of Ethyl Acetate and Benzaldehyde 384
Preparation of N-Ethyl-m-Toluidine from mToluidine and Ethyl Bromide 388 Microscale Gabriel Synthesis of Phthalimidoacetophenone 389 Synthesis of Acetanilide from Nitrobenzene 390
Diazonium Reactions Application: Natural and Synthetic Dyes 394 Experiment 41.1: Synthesis of Methyl Orange: Diazonium Coupling
391
Contents
Experiment 41.2:
XJ
Reaction of Sulfanilic Acid and N,NDimethylaniline 396 p-lodophenol from p-Aminophenol Using a Diazonium Salt 397
SECTION 42
Isocyanate Formation and Reactions Application: Uses of Polyurethanes 403 Experiment 42.1: Formation of Undecyl Isocyanate by Curtius Rearrangement and Its Reaction with Methanol 404
Preparation of 2,5-Dimethyl-1Phenylpyrrole 412 Preparation of 4-Methyl-2-Quinolinone Preparation of Benzimidazole 413 Preparation of Benzofurazan-1 -Oxide Preparation of Barbituric Acid 415 Preparation of 3-Carbethoxycoumarin
413 414 415
417 Structure Determination of a Carbohydrate 420 422
Polymers Application: Plastics 425 427 Experiment 45.1 Polymerization of Styrene 428 Experiment 45.2 Formation of Nylon 6,10 Experiment 45.3 Preparation of Cellulose Triacetate Enzymes in Organic Synthesis Application: Wine Making 435 Experiment 46.1: Reduction of Vanillin by Yeast
428 430
436
SECTION 47
Bio- and Chemiluminescence Experiment 47.1: Synthesis and Chemiluminescence of Luminol 444
438
SECTION 48
Porphyrins Experiment 48.1:
445
SECTION 49
Synthesis and Metallation of a Porphyrin
Chiral Resolution Experiment 49.1: Resolution of Methylbenzylamine
448 450
453
SECTION 50
Computers in Chemistry Experiment 50.1: Online Chemical Information Retrieval Experiment 50.2: Use of Educational Software 456