EBK ORGANIC CHEMISTRY: PRINCIPLES AND M
EBK ORGANIC CHEMISTRY: PRINCIPLES AND M
2nd Edition
ISBN: 9780393630817
Author: KARTY
Publisher: W.W.NORTON+CO. (CC)
Question
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Chapter 17, Problem 17.24P
Interpretation Introduction

(a)

Interpretation:

The detailed mechanism for the given reaction is to be drawn and the major product of the reaction is to be predicted.

Concept introduction:

The addition reaction mechanism dominates on whether the nucleophile adds to the carbonyl carbon reversibly or irreversibly. Nucleophilic addition is irreversible or reversible depends on charge stability. Nucleophilic addition tends to be irreversible if the negative charge that develops in the adduct is substantially better stabilized than it is in the nucleophile. Nucleophilic addition to a carbonyl carbon tends to be irreversible when it involves a very strong nucleophile like R- and H-. Otherwise, the nucleophile addition tends to be reversible. In α,β unsaturated carbonyl undergoes nucleophilic addition, Nucleophile that add reversibly to the carbonyl carbon yields the conjugate addition product as the major product and nucleophile that add irreversibly to the carbonyl carbon yield the direct addition product as the major product.

Expert Solution
Check Mark

Answer to Problem 17.24P

The major product and mechanism for the given reaction are:

EBK ORGANIC CHEMISTRY: PRINCIPLES AND M, Chapter 17, Problem 17.24P , additional homework tip  1

Explanation of Solution

The nucleophile CH3S- is less reactive and adds reversibly to the cyclohex-2-en-1-one. The nucleophile adds reversibly to the carbonyl carbon yield the conjugate addition (1, 4 addition) product.

In the first step, CH3S- nucleophile from CH3SNa add on the β carbon of the cyclohex-2-en-1-one. This generates an enolate anion.

EBK ORGANIC CHEMISTRY: PRINCIPLES AND M, Chapter 17, Problem 17.24P , additional homework tip  2

In the second step, this enolate anion is then protonated by an acid workup.

EBK ORGANIC CHEMISTRY: PRINCIPLES AND M, Chapter 17, Problem 17.24P , additional homework tip  3

In the last step, tautomerization takes place and produces a ketone with a conjugate addition product.

EBK ORGANIC CHEMISTRY: PRINCIPLES AND M, Chapter 17, Problem 17.24P , additional homework tip  4

Conclusion

Nucleophilic addition of CH3S- to the α,β unsaturated carbonyl produces the major product of the reaction via conjugate addition (1, 4 addition) of the nucleophile.

Interpretation Introduction

(b)

Interpretation:

The detailed mechanism for the given reaction is to be drawn and the major product of the reaction is to be predicted.

Concept introduction:

The addition reaction mechanism dominates on whether the nucleophile adds to the carbonyl carbon reversibly or irreversibly. Nucleophilic addition is irreversible or reversible depends on charge stability. Nucleophilic addition tends to be irreversible if the negative charge that develops in the adduct is substantially better stabilized than it is in the nucleophile. Nucleophilic addition to a carbonyl carbon tends to be irreversible when it involves a very strong nucleophile like R- and H-. Otherwise, the nucleophile addition tends to be reversible. In α,β unsaturated carbonyl undergoes nucleophilic addition, Nucleophile that add reversibly to the carbonyl carbon yields the conjugate addition product as the major product and nucleophile that add irreversibly to the carbonyl carbon yield the direct addition product as the major product.

Expert Solution
Check Mark

Answer to Problem 17.24P

The major product and detailed mechanism for the given reaction are:

EBK ORGANIC CHEMISTRY: PRINCIPLES AND M, Chapter 17, Problem 17.24P , additional homework tip  5

Explanation of Solution

The given nucleophile ylide is highly reactive and adds irreversibly to the cyclohex-2-en-1-one. The nucleophile adds irreversibly to the carbonyl carbon yield the direct addition (1, 2 addition) product.

In the first step, the given highly reactive ylide attack on the carbonyl carbon of the cyclohex-2-en-1-one and generates an anion. It is also called betaine formation.

EBK ORGANIC CHEMISTRY: PRINCIPLES AND M, Chapter 17, Problem 17.24P , additional homework tip  6

In the second step, the anion coordinates with PPh3 and formed an Oxaphosphetane.

EBK ORGANIC CHEMISTRY: PRINCIPLES AND M, Chapter 17, Problem 17.24P , additional homework tip  7

In the last step, Eliminates Ph3PO and get direct addition product.

EBK ORGANIC CHEMISTRY: PRINCIPLES AND M, Chapter 17, Problem 17.24P , additional homework tip  8

Conclusion

Nucleophilic addition of ylide (Wittig reagent) to the α,β unsaturated carbonyl produces the major product of the reaction via direct addition (1, 2 addition) of the nucleophile.

Interpretation Introduction

(c)

Interpretation:

The detailed mechanism for the given reaction is to be drawn and the major product of the reaction is to be predicted.

Concept introduction:

The addition reaction mechanism dominates on whether the nucleophile adds to the carbonyl carbon reversibly or irreversibly. Nucleophilic addition is irreversible or reversible depends on charge stability. Nucleophilic addition tends to be irreversible if the negative charge that develops in the adduct is substantially better stabilized than it is in the nucleophile. Nucleophilic addition to a carbonyl carbon tends to be irreversible when it involves a very strong nucleophile like R- and H-. Otherwise, the nucleophile addition tends to be reversible. In α,β unsaturated carbonyl undergoes nucleophilic addition, Nucleophile that add reversibly to the carbonyl carbon yields the conjugate addition product as the major product and nucleophile that add irreversibly to the carbonyl carbon yield the direct addition product as the major product.

Expert Solution
Check Mark

Answer to Problem 17.24P

The major product and detailed mechanism for the given reaction are:

EBK ORGANIC CHEMISTRY: PRINCIPLES AND M, Chapter 17, Problem 17.24P , additional homework tip  9

Explanation of Solution

The nucleophile HCOCH2- is less reactive and adds reversibly to the cyclohex-2-en-1-one. The nucleophile adds reversibly to the carbonyl carbon yield the conjugate addition (1, 4 addition) product.

In the first step, HCOCH2- nucleophile adds on the β carbon of the cyclohex-2-en-1-one. This generates an enolate anion.

EBK ORGANIC CHEMISTRY: PRINCIPLES AND M, Chapter 17, Problem 17.24P , additional homework tip  10

In the second step, this enolate anion is then protonated by an acid workup.

EBK ORGANIC CHEMISTRY: PRINCIPLES AND M, Chapter 17, Problem 17.24P , additional homework tip  11

In the last step, tautomerization takes place and produces a ketone with a conjugate addition product.

EBK ORGANIC CHEMISTRY: PRINCIPLES AND M, Chapter 17, Problem 17.24P , additional homework tip  12

Conclusion

Nucleophilic addition of HCOCH2- to the α,β unsaturated carbonyl produces the major product of the reaction via conjugate addition (1, 4 addition) of nucleophile.

Interpretation Introduction

(d)

Interpretation:

The detailed mechanism for the given reaction is to be drawn and the major product of the reaction is to be predicted.

Concept introduction:

The addition reaction mechanism dominates on whether the nucleophile adds to the carbonyl carbon reversibly or irreversibly. Nucleophilic addition is irreversible or reversible depends on charge stability. Nucleophilic addition tends to be irreversible if the negative charge that develops in the adduct is substantially better stabilized than it is in the nucleophile. Nucleophilic addition to a carbonyl carbon tends to be irreversible when it involves a very strong nucleophile like R- and H-. Otherwise, the nucleophile addition tends to be reversible. In α,β unsaturated carbonyl undergoes nucleophilic addition, Nucleophile that add reversibly to the carbonyl carbon yields the conjugate addition product as the major product and nucleophile that add irreversibly to the carbonyl carbon yield the direct addition product as the major product.

Expert Solution
Check Mark

Answer to Problem 17.24P

EBK ORGANIC CHEMISTRY: PRINCIPLES AND M, Chapter 17, Problem 17.24P , additional homework tip  13

Explanation of Solution

The given nucleophile C6H5- is highly reactive and adds irreversibly to the cyclohex-2-en-1-one. The nucleophile adds irreversibly to the carbonyl carbon yield the direct addition (1, 2 addition) product

In the first step, C6H5- nucleophile adds on the carbonyl carbon of the cyclohex-2-en-1-one. This generates an anion.

EBK ORGANIC CHEMISTRY: PRINCIPLES AND M, Chapter 17, Problem 17.24P , additional homework tip  14

In the second step, this anion is then protonated by acid workup and formed a direct addition product.

EBK ORGANIC CHEMISTRY: PRINCIPLES AND M, Chapter 17, Problem 17.24P , additional homework tip  15

Conclusion

Nucleophilic addition of Grignard reagent to the α,β unsaturated carbonyl produces the major product of the reaction via direct addition (1, 2 addition) of the nucleophile.

Interpretation Introduction

(e)

Interpretation:

The detailed mechanism for the given reaction is to be drawn and the major product of the reaction is to be predicted.

Concept introduction:

The addition reaction mechanism dominates on whether the nucleophile adds to the carbonyl carbon reversibly or irreversibly. Nucleophilic addition is irreversible or reversible depends on charge stability. Nucleophilic addition tends to be irreversible if the negative charge that develops in the adduct is substantially better stabilized than it is in the nucleophile. Nucleophilic addition to a carbonyl carbon tends to be irreversible when it involves a very strong nucleophile like R- and H-. Otherwise, the nucleophile addition tends to be reversible. In α,β unsaturated carbonyl undergoes nucleophilic addition, Nucleophile that add reversibly to the carbonyl carbon yields the conjugate addition product as the major product and nucleophile that add irreversibly to the carbonyl carbon yield the direct addition product as the major product.

Expert Solution
Check Mark

Answer to Problem 17.24P

EBK ORGANIC CHEMISTRY: PRINCIPLES AND M, Chapter 17, Problem 17.24P , additional homework tip  16

Explanation of Solution

The given nucleophile H- is highly reactive and adds irreversibly to the cyclohex-2-en-1-one. The nucleophile adds irreversibly to the carbonyl carbon yield the direct addition (1, 2 addition) product

In the first step, H- nucleophile adds on the carbonyl carbon of the cyclohex-2-en-1-one. This generates an anion.

EBK ORGANIC CHEMISTRY: PRINCIPLES AND M, Chapter 17, Problem 17.24P , additional homework tip  17

In the second step, this anion is then protonated by acid workup and formed a direct addition product.

EBK ORGANIC CHEMISTRY: PRINCIPLES AND M, Chapter 17, Problem 17.24P , additional homework tip  18

Conclusion

Nucleophilic addition of H- to the α,β unsaturated carbonyl produces the major product of the reaction via direct addition (1, 2 addition) of the nucleophile.

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Chapter 17 Solutions

EBK ORGANIC CHEMISTRY: PRINCIPLES AND M

Ch. 17 - Prob. 17.11PCh. 17 - Prob. 17.12PCh. 17 - Prob. 17.13PCh. 17 - Prob. 17.14PCh. 17 - Prob. 17.15PCh. 17 - Prob. 17.16PCh. 17 - Prob. 17.17PCh. 17 - Prob. 17.18PCh. 17 - Prob. 17.19PCh. 17 - Prob. 17.20PCh. 17 - Prob. 17.21PCh. 17 - Prob. 17.22PCh. 17 - Prob. 17.23PCh. 17 - Prob. 17.24PCh. 17 - Prob. 17.25PCh. 17 - Prob. 17.26PCh. 17 - Prob. 17.27PCh. 17 - Prob. 17.28PCh. 17 - Prob. 17.29PCh. 17 - Prob. 17.30PCh. 17 - Prob. 17.31PCh. 17 - Prob. 17.32PCh. 17 - Prob. 17.33PCh. 17 - Prob. 17.34PCh. 17 - Prob. 17.35PCh. 17 - Prob. 17.36PCh. 17 - Prob. 17.37PCh. 17 - Prob. 17.38PCh. 17 - Prob. 17.39PCh. 17 - Prob. 17.40PCh. 17 - Prob. 17.41PCh. 17 - Prob. 17.42PCh. 17 - Prob. 17.43PCh. 17 - Prob. 17.44PCh. 17 - Prob. 17.45PCh. 17 - Prob. 17.46PCh. 17 - Prob. 17.47PCh. 17 - Prob. 17.48PCh. 17 - Prob. 17.49PCh. 17 - Prob. 17.50PCh. 17 - Prob. 17.51PCh. 17 - Prob. 17.52PCh. 17 - Prob. 17.53PCh. 17 - Prob. 17.54PCh. 17 - Prob. 17.55PCh. 17 - Prob. 17.56PCh. 17 - Prob. 17.57PCh. 17 - Prob. 17.58PCh. 17 - Prob. 17.59PCh. 17 - Prob. 17.60PCh. 17 - Prob. 17.61PCh. 17 - Prob. 17.62PCh. 17 - Prob. 17.63PCh. 17 - Prob. 17.64PCh. 17 - Prob. 17.65PCh. 17 - Prob. 17.66PCh. 17 - Prob. 17.67PCh. 17 - Prob. 17.68PCh. 17 - Prob. 17.69PCh. 17 - Prob. 17.70PCh. 17 - Prob. 17.71PCh. 17 - Prob. 17.72PCh. 17 - Prob. 17.73PCh. 17 - Prob. 17.74PCh. 17 - Prob. 17.75PCh. 17 - Prob. 17.76PCh. 17 - Prob. 17.77PCh. 17 - Prob. 17.78PCh. 17 - Prob. 17.79PCh. 17 - Prob. 17.80PCh. 17 - Prob. 17.81PCh. 17 - Prob. 17.82PCh. 17 - Prob. 17.83PCh. 17 - Prob. 17.84PCh. 17 - Prob. 17.1YTCh. 17 - Prob. 17.2YTCh. 17 - Prob. 17.3YTCh. 17 - Prob. 17.4YTCh. 17 - Prob. 17.5YTCh. 17 - Prob. 17.6YTCh. 17 - Prob. 17.7YTCh. 17 - Prob. 17.8YTCh. 17 - Prob. 17.9YTCh. 17 - Prob. 17.10YTCh. 17 - Prob. 17.11YTCh. 17 - Prob. 17.12YTCh. 17 - Prob. 17.13YTCh. 17 - Prob. 17.14YT
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