Chapter 13 Alcohols Review of Concepts carbonyl group agent Grignard reagents groups oxidation

Chapter 13 Alcohols Review of Concepts Fill in the blanks below. To verify that your answers are correct, look in your textbook at the end of Chapter ...
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Chapter 13 Alcohols Review of Concepts Fill in the blanks below. To verify that your answers are correct, look in your textbook at the end of Chapter 13. Each of the sentences below appears verbatim in the section entitled Review of Concepts and Vocabulary. • • • • • • •



• •

• • • • • •

When naming an alcohol, the parent is the longest chain containing the __________ group. The conjugate base of an alcohol is called an ____________ ion. Several factors determine the relative acidity of alcohols, including ___________, ____________, and _______________________. The conjugate base of phenol is called a ____________, or _____________ ion. When preparing an alcohol via a substitution reaction, primary substrates will require SN___ conditions, while tertiary substrates will require SN___ conditions. Alcohols can be formed by treating a carbonyl group (C=O bond) with a ______________ agent. Grignard reagents are carbon nucleophiles that are capable of attacking a wide range of _________________, including the carbonyl group of ketones or aldehydes, to produce an alcohol. _______________ groups, such as the trimethylsilyl group, can be used to circumvent the problem of Grignard incompatibility and can be easily removed after the desired Grignard reaction has been performed. Tertiary alcohols will undergo an SN___ reaction when treated with a hydrogen halide. Primary and secondary alcohols will undergo an SN___ process when treated with either HX, SOCl2, PBr3, or when the hydroxyl group is converted into a tosylate group followed by nucleophilic attack. Tertiary alcohols undergo E1 elimination when treated with __________. Primary alcohols undergo oxidation twice to give a _____________________. Secondary alcohols are oxidized only once to give a ___________ PCC is used to convert a primary alcohol into an _____________. NADH is a biological reducing agent that functions as a ____________ delivery agent (very much like NaBH4 or LAH), while NAD+ is an _____________ agent. The are two key issues to consider when proposing a synthesis is whether there is: 1. a change in the ___________________. 2. a change in the ____________________.

CHAPTER 13

275

Review of Skills Fill in the blanks and empty boxes below. To verify that your answers are correct, look in your textbook at the end of Chapter 13. The answers appear in the section entitled SkillBuilder Review. 13.1 Naming an Alcohol PROVIDE A SYSTEMATIC NAME FOR THE FOLLOWING COMPOUND 1) IDENTIFY THE PARENT

Cl

Cl

2) IDENTIFY AND NAME SUBSTITUENTS 3) ASSIGN LOCANTS TO EACH SUBSTITUENT 4) ALPHABETIZE

OH

5) ASSIGN CONFIGURATION

13.2 Comparing the Acidity of Alcohols FOR EACH PAIR OF COMPOUNDS BELOW, CIRCLE THE COMPOUND THAT IS MORE ACIDIC:

OH

OH

Cl OH

Cl

OH

OH

Cl

OH

13.3 Identifying Oxidation and Reduction Reactions IN THE FOLLOWING REACTION, DETERMINE WHETHER THE STARTING MATERIAL HAS BEEN OXIDIZED, REDUCED, OR NEITHER:

O

RO OR

13.4 Drawing a Mechanism, and Predicting the Products of Hydride Reductions COMPLETE THE MECHANISM BELOW BY DRAWING ALL CURVED ARROWS, INTERMEDIATES AND PRODUCTS.

H H Al

O

H H

H

13.5 Preparing an Alcohol via a Grignard Reaction IDENTIFY REAGENTS THAT CAN ACHIEVE EACH OF THE FOLLOWING TRANSFORMATIONS

O Ph

1)

Et O

Ph

OH

1)

Me O

Me

2)

2)

1)

Et

2)

Ph

Et Me

O

H

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CHAPTER 13

13.6 Proposing Reagents for the Conversion of an Alcohol into an Alkyl Halide IDENTIFY REAGENTS THAT CAN ACHIEVE EACH OF THE FOLLOWING TRANSFORMATIONS

OH

Cl 1) 2)

13.7 Predicting the Products of an Oxidation Reaction DRAW THE EXPECTED PRODUCT OF THE FOLLOWING REACTION

OH

CrO3 H3 O + acetone

13.8 Converting Functional Groups IDENTIFY REAGENTS THAT CAN ACHIEVE EACH OF THE FOLLOWING FUNCTIONAL GROUP TRANSFORMATIONS

O

OH

X

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277

13.9 Proposing a Synthesis AS A GUIDE FOR PROPOSING A SYNTHESIS, ASK THE FOLLOWING TWO QUESTIONS: 1) IS THERE A CHANGE IN THE ______________ SKELETON? 2) IS THERE A CHANGE IN THE LOCATION OR IDENTITY OF THE _________________________? AFTER PROPOSING A SYNTHESIS, USE THE FOLLOWING TWO QUESTIONS TO ANALYZE YOUR ANSWER: 1) IS THE ________________________ OUTCOME OF EACH STEP CORRECT? 2) IS THE ________________________ OUTCOME OF EACH STEP CORRECT?

Review of Reactions Identify the reagents necessary to achieve each of the following transformations. To verify that your answers are correct, look in your textbook at the end of Chapter 13. The answers appear in the section entitled Review of Reactions. Preparation of Alkoxides ROH

RO

Na

Preparation of Alcohols via Reduction

R

R

H

O R

H

O

O

H H

OH R

R

R

O R

OH

R

OH

O R

OH

R

OMe

Preparation of Alcohols via Grignard Reagents O

OH R OH

O R

OMe

R

R

R

+ MeOH

278

CHAPTER 13

Protection and Deprotection of Alcohols

R OH

R O TMS

SN1 Reactions with Alcohols R

R OH

R R

R R

X

+ H2O

SN2 Reactions with Alcohols

OH

Br

OH

Cl

E1 and E2 Reactions with Alcohols OH

+

OH

OTs

Oxidation of Alcohols and Phenols OH R

R

O R

R

H2O

CHAPTER 13

OH R

279

O R

OH

OH

O

O

OH R

O R

H

Solutions 13.1. a) 5,5-dibromo-2-methylhexan-2-ol b) (2S,3R)-2,3,4-trimethylpentan-1-ol c) 2,2,5,5-tetramethylcyclopentanol d) 2,6-diethylphenol e) (S)-2,2,4,4-tetramethylcyclohexanol 13.2. OH

Br

a)

b)

Br

OH OH

c)

13.3. Nonyl mandelate has a longer alkyl chain than octyl mandelate and is therefore more effective at penetrating cell membranes, rendering it a more potent agent. Nonyl mandelate has a shorter alkyl chain than decyl mandelate and is therefore more watersoluble, enabling it to be transported through aqueous media and to reach its target destination more effectively.

280

CHAPTER 13

13.4. OH

O

Na

Na

a) NaH

OH

O

Na

b) OH

Li

O

Li

c) OH

O

Na

NaH

d)

13.5. F F OH

a) The electron-withdrawing effects of the fluorine atoms stabilize the conjugate base. OH

b) The conjugate base of a primary alcohol will be more easily solvated than the conjugate base of a tertiary alcohol. Cl Cl

OH

Cl

Cl

Cl c) The electron-withdrawing effects of the chlorine atoms stabilize the conjugate base.

O

OH d) The conjugate base is more highly stabilized by resonance, with the negative charge spread over two oxygen atoms, rather than just one oxygen atom.

CHAPTER 13

281

OH

e) The conjugate base is stabilized by resonance.

13.6. 2-nitrophenol is expected to be more acidic (lower pKa) because the conjugate base has a resonance structure in which the negative charge is spread onto an oxygen atom of the nitro group, shown below. In contrast, 3-nitrophenol does not have such a resonance structure: O

O

O N

O N

O

O

13.7. Br

H2 O

OH

a) b)

Br

NaOH

dilute H2SO4

OH

OH

c) 1) BH3 THF

d)

OH

2) H2O2, NaOH

OH 1) Hg(OAc)2, H2O

e)

2) NaBH4

1) BH3 THF

f)

2) H2O2, NaOH

HO

282

CHAPTER 13

13.8 1) BH3 THF

OH

2) H2O2, NaOH

a)

OH 1) Hg(OAc)2, H2O 2) NaBH4

b)

OH

dilute H2SO4

c)

13.9. a) (+2)  (+2). The starting material is neither oxidized nor reduced. b) (+1)  (+3). The starting material is oxidized. c) (+3)  (-1). The starting material is reduced. d) (+3)  (+3). The starting material is neither oxidized nor reduced. e) (0)  (+2). The starting material is oxidized. f) (+2)  (+3). The starting material is oxidized. 13.10. One carbon atom is reduced from an oxidation state of 0 to an oxidation state of -1, while the other carbon atom is oxidized from an oxidation state of 0 to an oxidation state of +1. Overall, the starting material does not undergo a net change in oxidation state and is, therefore, neither reduced nor oxidized. 13.11. One carbon atom is reduced from an oxidation state of 0 to an oxidation state of -2, while the other carbon atom is oxidized from an oxidation state of 0 to an oxidation state of +2. Overall, the starting material does not undergo a net change in oxidation state and is, therefore, neither reduced nor oxidized. 13.12. a) O

O

O H H

H Al H H

H

H

O H

H

H

H

H

CHAPTER 13

283

b) O O

O

H

O

H

H

H

H

H

H Al H H

c) O

O H

B

H

Me H

H

H H

O

O

H

H

d) O

O

O H

H

H

O H

H

H

H

H

H H Al H H

e) O

O O

H

O

O O

H

H

H

O

O H

H

H

H Al H

H Al

H

H

H

f) O

O

O OMe

H H

B H

H

H O

HO

O OMe

H

Me

H H

H

H O

OMe

H

284

CHAPTER 13

13.13. H

O

H

H Al H

O

O

O

H

O

H

H Al

H

H

H

H O

O H

H

OH

13.14. a) 1) MeMgBr

H

2) H2O O

OH

1) PrMgBr 2) H2O

H

b) O

1) MeMgBr 2) H2O

O

OH

1) PrMgBr 2) H2O

c) O H

1) PrMgBr H

2) H2O

OH

H H

OH

O

O

H

H

H H

H

O

HO

O

O H

H

CHAPTER 13

285

d) O

1) EtMgBr H

2) H2O OH

O

1)

H

MgBr

2) H2O

e) 1) MeMgBr 2) H2O

O

1) EtMgBr 2) H2O

O

OH

1) BuMgBr 2) H2O

O

f) 1) MeMgBr

O

2) H2O OH

O

1)

MgBr

2) H2O

13.15 Each of the following two compounds can be prepared from the reaction between a Grignard reagent and an ester, because each of these compounds has two identical groups connected to the α position: Me OH

OH

Me

The other four compounds from Problem 13.14 do not contain two identical groups connected to the α position, and cannot be prepared from the reaction between an ester and a Grignard reagent.

286

CHAPTER 13

13.16 Each of the following three compounds can be prepared from the reaction between a hydride reducing agent (NaBH4 or LAH) and a ketone or aldehyde, because each of these compounds has a hydrogen atom connected to the α position: OH

OH

OH

The other three compounds from Problem 13.14 do not contain a hydrogen atom connected to the α position and, therefore, cannot be prepared from the reaction between a hydride reducing agent (NaBH4 or LAH) and a ketone or aldehyde. 13.17.

H H C H

O O

MgBr O

O

CH3

CH3

O

O

H H C H H OH

H

O H

CH3

MgBr

O

H

O H

CH3

O

H

CH3 OH

CH3 OH

CH3 O

CH3

In this case, H3O+ must be used as a proton source because water is not sufficiently acidic to protonate a phenolate ion (see Section 13.2, Acidity of Alcohols and Phenols).

13.18. a) OH HO

Br

TMSCl, Et3N

TMSO

Br

1) Mg

TMSO

O 2) TBAF

3) H2O

OH HO

CHAPTER 13

287

b) Br

HO

TMSCl, Et3N

Br

TMSO

1) Mg O 2) OMe (0.5 equivalents) 3) H2O OH

OH HO

TBAF

OH

13.19. a) 1) TsCl, py OH

Br

2) NaBr

PBr3

b) Br

OH HBr

c) 1) TsCl, py 2) NaCl Cl

OH SOCl2 py

TMSO

OTMS

288

CHAPTER 13

d) 1) TsCl, py 2) NaBr Br

OH PBr3

e) 1) TsCl, py 2) NaCl OH

Cl SOCl2 py

f) 1) TsCl, py 2) NaBr HBr

OH

Br PBr3

13.20. 1) TsCl, py OH

NaCl

I

2) NaI

13.21. a) OH

H2SO4 +

heat major

b) OH

1) TsCl, py 2) NaOEt

minor

Cl

CHAPTER 13

13.22. a) HO

O

PCC CH2Cl2

H

O

O

H

H

b) O OH

OH Na2Cr2O7 H2SO4 , H2O

c) O H

xs CrO3

OH

HO

H3 O+ acetone

O

OH O

c) H OH

O PCC CH2Cl2

e) OH

PCC CH2Cl2

O

f) OH

Na2Cr2O7 H2SO4 , H2O

O

13.23. a) O 1) NaOH Br

H

2) PCC, CH2Cl2

b) 1) BH3 THF 2) H2O2, NaOH 3) PCC, CH2Cl2

O H

289

290

CHAPTER 13

c) 1) dilute H2SO4 2) Na2Cr2O7, H2SO4 , H2O

O

1) Br2 2) xs NaNH2 3) H2O 4) H2SO4, H2O, HgSO4

d) 1) Hg(OAc)2, H2O 2) NaBH4 3) Na2Cr2O7, H2SO4 , H2O

O

1) Br2 2) xs NaNH2 3) H2O 4) H2SO4, H2O, HgSO4

13.24. a) 1) H2, Lindlar's Catalyst 2) BH3 THF OH

3) H2O2, NaOH 1) 9-BBN 2) H2O2, NaOH 3) LAH 4) H2O

b) H2SO4, heat 1) Br2

OH 1) TsCl, py 2) t-BuOK

2) xs NaNH2 3) H2O

CHAPTER 13

d) 1) BH3 THF

O

2) H2O2, NaOH

H

3) PCC, CH2Cl2

e) 1) H2SO4, heat 2) H2, Pt OH

1) TsCl, py 2) NaOEt 3) H2, Pt

f) H2SO4, heat O

1) LAH H

OH

2) H2O

1) TsCl, py 2) t-BuOK

g) H2SO4, heat O

1) LAH 2) H2O

OH 1) TsCl, py 2) NaOEt

13.25. OH

H2SO4, heat

1) TsCl, py 2) NaOEt

13.26. H2SO4, heat OH

1) BH3 THF 1) TsCl, py 2) NaOEt

2) H2O2, NaOH

OH

291

292

CHAPTER 13

13.27. 1) EtMgBr 2) H2O

O H

a)

O

3) Na2Cr2O7 , H2SO4 , H2O

1) MeMgBr 2) H2O

O H

b)

O

3) Na2Cr2O7 , H2SO4 , H2O

13.28. a) 1) Br2 2) xs NaNH2 3) H2O

1) 9-BBN 2) H2O2, NaOH H O

1) BH3 THF

OH

PCC CH2Cl2

2) H2O2, NaOH

1) MeMgBr 2) H2O

O

3) Na2Cr2O7, H2SO4, H2O

b) 1) NaNH2 2)

1) 9-BBN I

O H

2) H2O2, NaOH

1) EtMgBr 2) H2O 3) Na2Cr2O7 , H2SO4 , H2O O

c) 1) EtMgBr 2) H2O

O H

3) Na2Cr2O7 , H2SO4 , H2O

O

293

CHAPTER 13

d) OH 1) TsCl, py

1) BH3 THF

2) t-BuOK

2) H2O2, NaOH

OH

PCC, CH2Cl2 1) MeMgBr 2) H2O

H

3) Na2Cr2O7 , H2SO4 , H2O

O

O

e) H

1) 9-BBN O

2) H2O2, NaOH

1) MeMgBr 2) H2O 3) Na2Cr2O7 , H2SO4 , H2O

O

f) OH

1) Na2Cr2O7 , H2SO4 , H2O

OH

2) MeMgBr 3) H2O

13.29. a) O

1) MeMgBr

OH

2) H2O

H

b) dilute H2SO4

H2

H C C

Na

Lindlar's Catalyst

Br OH

1) Mg O 2) H 3) H2O

1) LAH

H2SO4, H2O HgSO4

2) H2O O

294

CHAPTER 13

c) 1) HBr, ROOR 2) NaOH

H2

H C C

Lindlar's Catalyst

Na

Br

OH 1) 9-BBN

O

1) LAH H

2) H2O2, NaOH

2) H2O

d) H C C

O

Na

1) 9-BBN

Br

1) EtMgBr H

2) H2O2, NaOH

2) H2O

1) NaNH2 2) EtBr H2SO4, H2O HgSO4

13.30. a) 2-propyl-1-pentanol b) (R)-4-methyl-2-pentanol c) 2-bromo-4-methylphenol d) (1R,2R)-2-methylcyclohexanol 13.31. a) OH OH

b) OH

c) OH O2N

NO2

NO2

O

1) LAH 2) H2O

OH

CHAPTER 13

d)

OH

e)

f)

HO

OH

HO

13.32. OH

OH

HO

OH

1-butanol

2-butanol

2-methyl-2-propanol

13.33. a) Increasing acidity Cl

OH

Cl Cl

Cl Cl

Cl

Cl

Cl Cl

OH

OH

b) Increasing acidity

OH

OH

OH

c) Increasing acidity OH

OH

OH NO2

2-methyl-1-propanol

295

296

CHAPTER 13

13.34. a) O

O

O

O

O

b) O

O

c) O

O

13.35. a) 1-bromobutane

O

b) 1-chlorobutane

c) 1-chlorobutane

d) trans-2-butene

O

O

e)

H

f)

OH

g)

i)

OTMS

j)

OTs

k)

O

Li

O

Na

O

h)

O

l)

Na

K

13.36. H H O H

H

13.37. a) OH

PCC CH2Cl2

O H

O

H

H O H

H

O

H

OH

CHAPTER 13

b) OH

Na2Cr2O7

O

H2SO4 , H2O

OH

c) OH

OH

1) PCC, CH2Cl2 2) EtMgBr 3) H2O

d) OH

1) PCC, CH2Cl2 2) EtMgBr 3) H2O

OH

4) Na2Cr2O7, H2SO4 , H2O 5) MeMgBr 6) H2O

e) OH

1) PCC, CH2Cl2 2) PrMgBr 3) H2O 4) Na2Cr2O7, H2SO4 , H2O

O

13.38. a) 1)

MgBr

O H

OH 2) H2O

H

b) O 1) MeMgBr 2) H2O OH

O 1) PrMgBr 2) H2O O

1) 2) H2O

MgBr

297

298

CHAPTER 13

c) O

1) EtMgBr H

O

2) H2O

OH

1) PrMgBr

H

2) H2O

d) 1) MeMgBr

O

2) H2O 1) EtMgBr

O

OH

2) H2O 1) PrMgBr

O

2) H2O

13.39. O

O

O

H

a)

O

b)

c)

13.40. a) O H

1) EtMgBr 2) H2O 3) Na2Cr2O7 , H2SO4 , H2O

O

d)

CHAPTER 13

b) 1) LAH 2) H2O

O

OH

H

NaBH4 MeOH

13.41.

Br

O

H

- Br

H

Br

O

O

13.42. The major product is 1-methylcyclohexanol (resulting from Markvonikov addition), which is a tertiary alcohol. Tertiary alcohols do not generally undergo oxidation. The minor product (2-methylcyclohexanol) is a secondary alcohol and can undergo oxidation to yield a ketone.

13.43. O Br

Mg

MgBr

OH

1)

H2SO4 heat

2) H2O Compound A

Compound B

Compound C

299

300

CHAPTER 13

13.44. O

OH 1) MeMgBr

H

2) H2O Na2Cr2O7 H2SO4, H2O O

OH 1) PhMgBr 2) H2O 1) TsCl, py 2) t-BuOK

OH 1) BH3 THF 2) H2O2, NaOH PBr3 OH Br 1) Mg O

2)

H

H

PCC CH2Cl2

3) H2O O H

13.45.

OH

1) TsCl

1) HBr, ROOR

2) NaOEt

2) Mg

Na2Cr2O7 H2SO4, H2O

O

1) PrMgBr 2) H2O

OH

301

CHAPTER 13

13.46. a) O

H

O

O

O H

H

H

H

H H Al H H

b) O

O

H

O H

HO

H

HO

H

H

H H Al H H

c) O

O

H

O H

Me

H H

B

H

H

13.47. a) OH

Cl

SOCl2 py

+ SO2

Cl Cl

S

Cl

O Cl H

O

S

O Cl

H

O

Cl S

Cl

N

O

O

S

O

+

Cl

302

CHAPTER 13

b) Br P Br OH

H

Br

O

Br P

Br

Br

SN2

+

+

Br

PBr2OH

c) O

O

O O

H

H

H

H

O

H

H

H

O

O

O

H

H

H

H

H Al H

H Al H

H

H

13.48. OH

OH

O

Na 2Cr2 O7 H 2SO4, H 2O

a)

b) O

PCC CH2Cl2

OH

c) O

e)

OH

H

OH

O

2) H2O

f)

13.49 a) 1) O3 2) DMS 3) Excess LAH 4) H2O

HO

OH

Na2 Cr 2 O7 H2 SO4, H2O

d)

1) LAH H

O

PCC CH2Cl2

1) LAH 2) H2O

O OH

OH

CHAPTER 13

b) 1) O3 2) DMS 3) Excess LAH

HO

OH

4) H2O

c) 1) O3 2) DMS 3) Excess LAH

HO

OH

4) H2O

d) 1) EtMgBr 2) H2O

O

OH

3) Na2Cr2O7 , H2SO4 , H2O

H

4) EtMgBr 5) H2O

e) 1) LAH 2) H2O O

3) TsCl , pyridine

OTs

H

f) 1) H3O+ 2) Na2Cr2O7 , H2SO4 , H2O 3) PhMgBr 4) H2O

OH Ph

13.50. a) O

H H C H

MgBr

H3C

O H

O

H3C H

OH

303

304

CHAPTER 13

b)

O O

H H C H

MgBr

O

H H C H

O

CH3 O

H

MgBr

O

CH3 CH3

O

O

H HO

CH3 CH3

O

O H

OH

H

CH3 CH3

O H

OH

13.51. O 1) 9-BBN 2) H2O2 , NaOH

H

PCC CH2Cl2

1) LAH 2) H2O

1) Br2 2) xs NaNH2 3) H2O

1) TsCl OH

PBr3

NaOH

2) NaOEt

1) BH3 THF 2) H2O2 , NaOH HBr, ROOR

Br

t-BuOK

H2 , Lindlar's Catalyst

CHAPTER 13

13.52. a) O H

O

1) MeMgBr 2) H2O 3) Na2Cr2O7 , H2SO4 , H2O

b) O H

1) LAH 2) H2O 3) TsCl, py 4) NaOEt

c) O H

1) LAH 2) H2O

O

3) TsCl, py 4) NaOEt 5) O3 6) DMS

d) O H

1) MeMgBr 2) H2O 3) TsCl, py 4) t-BuOK

e) 1) NaOH Cl

2) PCC, CH2Cl2

O H

f) 1) NaOH 2) PCC, CH2Cl2 Cl

3) MeMgBr 4) H2O 5) Na2Cr2O7 , H2SO4 , H2O

O

305

306

CHAPTER 13

g) O

1) dilute H2SO4 2) Na2Cr2O7 , H2SO4 , H2O

h) 1) dilute H2SO4 2) Na2Cr2O7 , H2SO4 , H2O

OH

3) MeMgBr 4) H2O

i) 1) dilute H2SO4 2) Na2Cr2O7 , H2SO4 , H2O 3) MeMgBr 4) conc. H2SO4, heat

j) OH

1) HgSO4, H2SO4, H2O 2) MeMgBr 3) H2O

k) 1) dilute H2SO4 2) Na2Cr2O7, H2SO4, H2O 3) MeMgBr 4) H2O

l) O

1) EtMgBr H

2) H2O

m) O

1) LAH 2) conc. H2SO4

OH

OH

CHAPTER 13

n) 1) LAH O

2) H2O 3) TsCl, Et3N 4) t-BuOK

o) 1) LAH 2) H2O

O

3) TsCl, Et3N

HO

4) t-BuOK 5) BH3 THF 6) H2O2, NaOH

p) 1) MeMgBr 2) H2O

O

3) conc. H2SO4, heat

q) O

1) EtMgBr

OH

2) H2O

r) O

1) LAH H

2) H2O

Br

3) PBr3

s) 1) BH3 THF 2) H2O2, NaOH 3) PCC, CH2Cl2 4) MeMgBr 5) H2O

OH

307

308

CHAPTER 13

13.53. HO

13.54. OH

13.55. OH

OH

13.56. OH

13.57 H

O

H

O

H Al H

O

O

H

H Al

H

O

H

O

O O

O

O

H

H

H

O

O

O

H O O

O H H Al H H H H Al

O

O

H

2

H

H

O

H

H

O

O

H

O O

H

O H

O HO

O H

H

OH

H

HO

O H

O O

309

CHAPTER 13

13.58 O O

H H C H

MgBr

O

CH3

O

CH3

O

O

O O

O

2 O

MgBr

O O

O

O MgBr

MgBr

CH3

O

CH3 H3C

O H3C

O O

H

O H

O

O HO

H

CH3 CH3

OH

H

CH3 CH3

HO

13.59 O

1) Br2, hv

1) BH3 THF

2) NaOMe

2) H2O2, NaOH 3) Na2Cr2O7, H2SO4, H2O 1) MeMgBr 2) H2O

OH H2 Pt

conc. H2SO4 heat

CH3 CH3

O

CH3 CH3

O O

H H C H

H H C H

CH3 CH3

O

O

O

H H C H

O O

310

CHAPTER 13

13.60. O O

O O

O

H

O

- CH3O O

O

O

H

H

H Al H

H Al H

H

H

H

O

H

H

- CH3O

H

O H

H

H Al H

O H

O

H

H

H

H

H

O

H

H

H

H

13.61. HO

O H O S O H O

OH

HO

H O H

- H2O

HO

methyl shift

O

H

O

H

H O

HO

13.62. One carbon atom is oxidized from an oxidation state of +1 to an oxidation state of +2, while the other carbon atom is reduced from an oxidation state of +1 to an oxidation state of 0. Overall, the starting material does not undergo a net change in oxidation state and is, therefore, neither reduced nor oxidized.

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