Organic Chemistry
Organic Chemistry
4th Edition
ISBN: 9780073402772
Author: Janice G. Smith
Publisher: MCG
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Chapter 12, Problem 12.40P

Draw the organic products formed when allylic alcoholA is treated with each reagent.

Chapter 12, Problem 12.40P, Draw the organic products formed when allylic alcoholA is treated with each reagent. a. H2+Pd-C b.

a. H 2 + Pd-C

b. mCPBA

c. PCC

d. CrO 3 , H 2 SO 4 , H 2 O

e. ( CH 3 ) 3 COOH , Ti [ OCH ( CH 3 ) 2 ] 4 , ( + ) -DET

f. ( CH 3 ) 3 COOH , Ti [ OCH ( CH 3 ) 2 ] 4 , ( ) -DET

g. [1] PBr 3 ; [2] LiAlH 4 ;[3] H 2 O

h. HCrO 4 -Amberlyst A- 26 resin

Expert Solution
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Interpretation Introduction

(a)

Interpretation: The product formed when A is treated with H2+Pd-C is to be predicted.

Concept introduction: The addition of H2 in presence of a catalyst is known as catalytic hydrogenation reaction. This is a syn addition. Alkyne is reduced to alkane. In this reaction, two weak pi bond of alkyne and sigma bond between H2 is broken and four CH bonds are formed.

Answer to Problem 12.40P

The product formed when A is treated with H2+Pd-C is shown in Figure 1.

Explanation of Solution

When A is treated with H2+Pd-C, the CC double bond is reduced to CC single bond. The product formed is 3-methyl-1-pentanol. The reaction is as follows,

Organic Chemistry, Chapter 12, Problem 12.40P , additional homework tip  1

Figure 1

Conclusion

The product formed when A is treated with H2+Pd-C is shown in Figure 1.

Expert Solution
Check Mark
Interpretation Introduction

(b)

Interpretation: The product formed when A is treated with mCPBA is to be predicted.

Concept introduction: In presence of peroxide alkene is oxidized to epoxide this is known as epoxidation. The weak pi bond of alkene and weak OO bond of peroxide are broken and two new CO bonds are formed. Breaking of bonds and formation of bonds takes place in single step. mCPBA is meta-chloroperoxybenzoicacid.

Answer to Problem 12.40P

The product formed when A is treated with mCPBA is shown in Figure 2.

Explanation of Solution

In the given reaction, when A is treated with mCPBA (meta-chloroperoxybenzoicacid), alkene is oxidized to epoxide. The product formed is 3-ethyl-3-methyloxiran-2-yl methanol. The reaction is as follows,

Organic Chemistry, Chapter 12, Problem 12.40P , additional homework tip  2

Figure 2

Conclusion

The product formed when A is treated with mCPBA is shown in Figure 2.

Expert Solution
Check Mark
Interpretation Introduction

(c)

Interpretation: The product formed when A is treated with PCC is to be predicted.

Concept introduction: Alcohols are oxidized to different carbonyl compounds depending upon the reagents and alcohol used. In presence of strong oxidizing reagents such as KMnO4,K2Cr2O7 and CrO3, primary alcohols are oxidized to carboxylic acids and secondary alcohols are oxidized to ketones. In presence of mild oxidizing agents such as PCC, primary alcohols are oxidized to aldehydes and secondary alcohols to ketones.

Answer to Problem 12.40P

The product formed when A is treated with PCC is shown in Figure 3.

Explanation of Solution

In the given reaction, when A is treated with PCC, the primary alcohol is oxidized to aldehyde. The corresponding chemical reaction is given below. The product formed is 3-methylpent-2-enal.

Organic Chemistry, Chapter 12, Problem 12.40P , additional homework tip  3

Figure 3

Conclusion

The product formed when A is treated with PCC is shown in Figure 3.

Expert Solution
Check Mark
Interpretation Introduction

(d)

Interpretation: The product formed when A is treated with CrO3,H2SO4,H2O is to be predicted.

Concept introduction: Alcohols are oxidized to different carbonyl compounds depending upon the reagents and alcohol used. In the presence of strong oxidizing reagents such as KMnO4,K2Cr2O7 and CrO3, primary alcohols are oxidized to carboxylic acids and secondary alcohols are oxidised to ketones. In the presence of mild oxidizing agents such as PCC, primary alcohols are oxidized to aldehydes and secondary alcohols to ketones.

Answer to Problem 12.40P

The product formed when A is treated with CrO3,H2SO4,H2O is shown in Figure 4.

Explanation of Solution

In the given reaction, when A is treated with CrO3,H2SO4,H2O, the primary alcohol is oxidized to carboxylic acid. The corresponding chemical reaction is given below. The product formed is 3-methylpent-2-enoic acid.

Organic Chemistry, Chapter 12, Problem 12.40P , additional homework tip  4

Figure 4

Conclusion

The product formed when A is treated with CrO3,H2SO4,H2O is shown in Figure 4.

Expert Solution
Check Mark
Interpretation Introduction

(e)

Interpretation: The product formed when A is treated with Sharpless reagent (+)-DET is to be predicted.

Concept introduction: Sharpless epoxidation involves the oxidation of double bond between carbon atoms to epoxide. This oxidation occurs only in allylic alcohol. This is an enantioselective oxidation, which means predominantly one enantiomer is formed. Sharpless reagents are tert-butylhydroperoxide,(CH3)3COOH; titanium (IV) isopropoxide, Ti[OCH(CH3)2]4; and diethyl tartrate.

Answer to Problem 12.40P

The product formed when A is treated with Sharpless reagent (+)-DET is shown in Figure 5.

Explanation of Solution

There are two different chiral diethyl tartrate isomers, (+)-DET and ()-DET to indicate the direction in which they rotate the plane polarized light. The configuration of isomer determines which enantiomer is the major product.

When epoxidation is done using (+)-DET, epoxide is formed from below the plane as shown below.

Organic Chemistry, Chapter 12, Problem 12.40P , additional homework tip  5

Figure 5

Conclusion

The product formed when A is treated with Sharpless reagent (+)-DET is shown in Figure 5

Expert Solution
Check Mark
Interpretation Introduction

(f)

Interpretation: The product formed when A is treated with Sharpless reagent ()-DET is to be predicted.

Concept introduction: Sharpless epoxidation involves the oxidation of double bond between carbon atoms to epoxide. This oxidation occurs only in allylic alcohol. This is an enantioselective oxidation, which means predominantly one enantiomer is formed. Sharpless reagents are tert-butylhydroperoxide,(CH3)3COOH; titanium (IV) isopropoxide, Ti[OCH(CH3)2]4; and diethyl tartrate.

Answer to Problem 12.40P

The product of formed when A is treated with Sharpless reagent ()-DET is shown in Figure 6.

Explanation of Solution

There are two different chiral diethyl tartrate isomers, (+)-DET and ()-DET to indicate the direction in which they rotate the plane polarized light. The configuration of isomer determines which enantiomer is the major product.

When epoxidation is done using ()-DET, epoxide is formed from below the plane as shown below.

Organic Chemistry, Chapter 12, Problem 12.40P , additional homework tip  6

Figure 6

Conclusion

The product formed when A is treated with Sharpless reagent ()-DET is shown in Figure 6

Expert Solution
Check Mark
Interpretation Introduction

(g)

Interpretation: The product formed when A is treated with given reagent is shown in Figure 7.

Concept introduction: Alcohols on treatment with phosphorus tribromide gives alkyl bromide. The CX bond in alkyl halides can be reduced using metal hydride reagents. The alkyl halides are reduced to alkanes with X acting as leaving group.

Answer to Problem 12.40P

The product formed in the given reaction is shown in Figure 7.

Explanation of Solution

The given reaction is,

Organic Chemistry, Chapter 12, Problem 12.40P , additional homework tip  7

Figure 7

When the given alcohol is treated with PBr3, it forms alkyl bromide. The alkyl bromide on further reaction with LiAlH4,H2O produces alkane. Hence, The final product is 3-methylpent-2-ene.

Conclusion

The product formed when A is treated with given reagent is shown in Figure 7.

Expert Solution
Check Mark
Interpretation Introduction

(h)

Interpretation: The product formed when A is treated with HCrO4-AmberlystA-26 resin is to be predicted.

Concept introduction: HCrO4-AmberlystA-26 is an insoluble polymeric reagent. It consists of complex hydrocarbon network with cationic ammonium ion which acts a counter ion to anionic chromium ion. This is a green chemistry method for oxidation of alcohols as it avoids the usage of strong acids and also it forms by-product with carcinogenic Cr3+ which can be removed by filtration.

Answer to Problem 12.40P

The product formed when A is treated with HCrO4-AmberlystA-26 resin is shown in Figure 8.

Explanation of Solution

In the given reaction, when A is treated with HCrO4-AmberlystA-26, the primary alcohol is oxidized to aldehyde. The corresponding chemical reaction is given below. The product formed is 3-methylpent-2-enal.

Organic Chemistry, Chapter 12, Problem 12.40P , additional homework tip  8

Figure 8

Conclusion

The product formed when A is treated with HCrO4-AmberlystA-26 resin is shown in Figure 8.

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Chapter 12 Solutions

Organic Chemistry

Ch. 12 - Problem 12.11 (a) Draw the structure of a compound...Ch. 12 - Prob. 12.12PCh. 12 - Prob. 12.13PCh. 12 - Prob. 12.14PCh. 12 - Prob. 12.15PCh. 12 - Prob. 12.16PCh. 12 - Prob. 12.17PCh. 12 - Problem 12.18 Draw the products formed when both...Ch. 12 - Prob. 12.19PCh. 12 - Prob. 12.20PCh. 12 - Prob. 12.21PCh. 12 - Prob. 12.22PCh. 12 - Prob. 12.23PCh. 12 - Problem 12.24 Draw the organic products in each of...Ch. 12 - Prob. 12.25PCh. 12 - Prob. 12.26PCh. 12 - Problem 12.27 Draw the products of each Sharpless...Ch. 12 - Prob. 12.28PCh. 12 - 12.29 Draw the products formed when A is treated...Ch. 12 - Prob. 12.30PCh. 12 - 12.31 Devise a synthesis of the following compound...Ch. 12 - Label each reaction as oxidation, reduction, or...Ch. 12 - Prob. 12.33PCh. 12 - Prob. 12.34PCh. 12 - Prob. 12.35PCh. 12 - Prob. 12.36PCh. 12 - 12.37 Stearidonic acid (C18H28O2) is an...Ch. 12 - Draw the organic products formed when cyclopentene...Ch. 12 - Prob. 12.39PCh. 12 - Draw the organic products formed when allylic...Ch. 12 - Draw the organic products formed in each reaction...Ch. 12 - Draw the organic products formed in each reaction....Ch. 12 - Prob. 12.43PCh. 12 - Prob. 12.44PCh. 12 - Prob. 12.45PCh. 12 - What alkene is needed to synthesize each 1,2-diol...Ch. 12 - Prob. 12.47PCh. 12 - Draw the products formed after Steps 1 and 2 in...Ch. 12 - Prob. 12.49PCh. 12 - Prob. 12.50PCh. 12 - Prob. 12.51PCh. 12 - What alkyne gives each set of products after...Ch. 12 - Prob. 12.53PCh. 12 - Prob. 12.54PCh. 12 - Prob. 12.55PCh. 12 - 12.54 An unknown compound A of molecular formula ...Ch. 12 - 12.55 DHA is a fatty acid derived from fish oil...Ch. 12 - Prob. 12.58PCh. 12 - Prob. 12.59PCh. 12 - 12.58 Epoxidation of the following allylic alcohol...Ch. 12 - What allylic alcohol and DET isomer are needed to...Ch. 12 - Devise a synthesis of each hydrocarbon from...Ch. 12 - Prob. 12.63PCh. 12 - 12.62 It is sometimes necessary to isomerize a cis...Ch. 12 - Prob. 12.65PCh. 12 - Prob. 12.66PCh. 12 - Prob. 12.67PCh. 12 - Prob. 12.68PCh. 12 - Devise a synthesis of each compound from the...Ch. 12 - Devise a synthesis of each compound from acetylene...Ch. 12 - Prob. 12.71PCh. 12 - Prob. 12.72PCh. 12 - Prob. 12.73PCh. 12 - Prob. 12.74PCh. 12 - Prob. 12.75PCh. 12 - Prob. 12.76PCh. 12 - 12.72 Draw a stepwise mechanism for the following...Ch. 12 - Prob. 12.78PCh. 12 - Prob. 12.79PCh. 12 - Prob. 12.80PCh. 12 - 12.75 Sharpless epoxidation of allylic alcohol X...
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