Organic Chemistry: Principles and Mechanisms (Second Edition)
Organic Chemistry: Principles and Mechanisms (Second Edition)
2nd Edition
ISBN: 9780393663556
Author: Joel Karty
Publisher: W. W. Norton & Company
Question
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Chapter 23, Problem 23.1P
Interpretation Introduction

(a)

Interpretation:

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

Concept introduction:

In the case of an electrophilic aromatic substitution reaction, a substituent influences the site of reaction. The electron-donating groups are ortho/para directing groups while electron-withdrawing groups are meta directing groups in the electrophilic aromatic substitution reaction. The Friedel-Crafts alkylation and acylation are an example of an electrophilic aromatic substitution reaction. The chlorination of the aromatic ring can be carried out by reacting with Cl2 in the presence of FeCl3, which is also an example of an electrophilic aromatic substitution reaction. In Friedel-Crafts reaction, the first step is the formation of an electrophile, and then the electrophilic addition-elimination takes place with the aromatic ring and the electrophile.

Expert Solution
Check Mark

Answer to Problem 23.1P

The major product for the given reaction is

Organic Chemistry: Principles and Mechanisms (Second Edition), Chapter 23, Problem 23.1P , additional homework tip  1

The complete, detailed mechanism for the given reaction is given below.

Formation of the electrophile:

Organic Chemistry: Principles and Mechanisms (Second Edition), Chapter 23, Problem 23.1P , additional homework tip  2

Formation of the product (a racemic mixture of ortho and para isomer):

For ortho isomer:

Organic Chemistry: Principles and Mechanisms (Second Edition), Chapter 23, Problem 23.1P , additional homework tip  3

For para isomer:

Organic Chemistry: Principles and Mechanisms (Second Edition), Chapter 23, Problem 23.1P , additional homework tip  4

Explanation of Solution

The given reaction is

Organic Chemistry: Principles and Mechanisms (Second Edition), Chapter 23, Problem 23.1P , additional homework tip  5

It is noticed that the given substrate, phenol, is treated with ethyl chloride in the presence of AlCl3 as a catalyst. So it is an example of the Friedel-Crafts alkylation reaction. Since the electron-donating OH group is directly attached to the benzene ring, which is ortho/para director in electrophilic aromatic substitution, the reaction leads to giving the racemic mixture of the product. Therefore, the products of the given reaction are

Organic Chemistry: Principles and Mechanisms (Second Edition), Chapter 23, Problem 23.1P , additional homework tip  6

The mechanism for the given reaction is given below.

Since the given reaction is an example of an electrophilic aromatic substitution reaction, the first step is the formation of the electrophile as given below.

Initially, the electron-rich chlorine of the ethyl chloride is coordinated with an electron-deficient aluminum of AlCl3 followed by heterolysis of C-Cl bond to form the corresponding ethyl cation, which is nothing but the required electrophile.

Organic Chemistry: Principles and Mechanisms (Second Edition), Chapter 23, Problem 23.1P , additional homework tip  7

The formed electrophile, ethyl cation (CH3-CH2+), then underdoes electrophilic addition to the benzene ring, followed by electrophilic elimination mechanism to form the ortho and para isomers shown below:

For ortho isomer:

Organic Chemistry: Principles and Mechanisms (Second Edition), Chapter 23, Problem 23.1P , additional homework tip  8

For para isomer:

Organic Chemistry: Principles and Mechanisms (Second Edition), Chapter 23, Problem 23.1P , additional homework tip  9

Conclusion

The major product for the given reaction is predicted, and the complete, detailed mechanism for the same reaction is drawn on the basis of the electrophilic aromatic substitution reaction.

Interpretation Introduction

(b)

Interpretation:

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

Concept introduction:

In the case of an electrophilic aromatic substitution reaction, a substituent influences the site of reaction. The electron-donating groups are ortho/para directing groups while electron-withdrawing groups are meta directing groups in the electrophilic aromatic substitution reaction. The Friedel-Crafts alkylation and acylation are an example of an electrophilic aromatic substitution reaction. The chlorination of the aromatic ring can be carried out by reacting with Cl2 in the presence of FeCl3, which is also an example of an electrophilic aromatic substitution reaction. In Friedel-Crafts reaction, the first step is the formation of an electrophile, and then the electrophilic addition-elimination takes place with the aromatic ring and the electrophile.

Expert Solution
Check Mark

Answer to Problem 23.1P

The major product for the given reaction is

Organic Chemistry: Principles and Mechanisms (Second Edition), Chapter 23, Problem 23.1P , additional homework tip  10

The complete, detailed mechanism for the given reaction is given below.

Formation of the electrophile:

Organic Chemistry: Principles and Mechanisms (Second Edition), Chapter 23, Problem 23.1P , additional homework tip  11

Formation of the product:

Organic Chemistry: Principles and Mechanisms (Second Edition), Chapter 23, Problem 23.1P , additional homework tip  12

Explanation of Solution

The given reaction is

Organic Chemistry: Principles and Mechanisms (Second Edition), Chapter 23, Problem 23.1P , additional homework tip  13

It is noticed that the given substrate is treated with Cl2 in the presence of FeCl3; it is an example of electrophilic aromatic substitution reaction. Since the nitro group is a meta director, the major product of the given reaction is m-chloronitrobenzene.

Organic Chemistry: Principles and Mechanisms (Second Edition), Chapter 23, Problem 23.1P , additional homework tip  14

The mechanism for the given reaction is given below.

Since the given reaction is an example of an electrophilic aromatic substitution reaction, the first step is the formation of the electrophile as given below.

Initially, one of the electron-rich chlorine atoms of Cl2 is coordinated with an electron-deficient iron metal of FeCl3, followed by heterolysis of Cl-Cl bond to form the corresponding cation, which is nothing but the required electrophile.

Organic Chemistry: Principles and Mechanisms (Second Edition), Chapter 23, Problem 23.1P , additional homework tip  15

The formed electrophile (Cl+) then underdoes electrophilic addition to the benzene ring, followed by electrophilic elimination mechanism, to form the major meta isomer as the product, as shown below:

Organic Chemistry: Principles and Mechanisms (Second Edition), Chapter 23, Problem 23.1P , additional homework tip  16

Conclusion

The major product for the given reaction is predicted, and the complete, detailed mechanism for the same reaction is drawn on the basis of the electrophilic aromatic substitution reaction.

Interpretation Introduction

(c)

Interpretation:

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

Concept introduction:

In the case of an electrophilic aromatic substitution reaction, a substituent influences the site of reaction. The electron-donating groups are ortho/para directing groups while electron-withdrawing groups are meta directing groups in the electrophilic aromatic substitution reaction. The Friedel-Crafts alkylation and acylation are an example of an electrophilic aromatic substitution reaction. The chlorination of the aromatic ring can be carried out by reacting with Cl2 in the presence of FeCl3, which is also an example of an electrophilic aromatic substitution reaction. In Friedel-Crafts reaction, the first step is the formation of an electrophile, and then the electrophilic addition-elimination takes place with the aromatic ring and the electrophile.

Expert Solution
Check Mark

Answer to Problem 23.1P

The major product for the given reaction is

Organic Chemistry: Principles and Mechanisms (Second Edition), Chapter 23, Problem 23.1P , additional homework tip  17

The complete, detailed mechanism for the given reaction is given below.

Formation of the electrophile:

Organic Chemistry: Principles and Mechanisms (Second Edition), Chapter 23, Problem 23.1P , additional homework tip  18

Formation of the product (a racemic mixture of ortho and para isomer):

For ortho isomer:

Organic Chemistry: Principles and Mechanisms (Second Edition), Chapter 23, Problem 23.1P , additional homework tip  19

For para isomer:

Organic Chemistry: Principles and Mechanisms (Second Edition), Chapter 23, Problem 23.1P , additional homework tip  20

Explanation of Solution

The given reaction is

Organic Chemistry: Principles and Mechanisms (Second Edition), Chapter 23, Problem 23.1P , additional homework tip  21

It is noticed that the given substrate, toluene, is treated with an acyl chloride in the presence of AlCl3 as a catalyst. So it is an example of Friedel-Crafts acylation reaction. Since the electron-donating CH3 group is directly attached to the benzene ring, which is ortho/para director in electrophilic aromatic substitution reaction, it leads to giving the mixture of the products. Therefore, the products of the given reaction are

Organic Chemistry: Principles and Mechanisms (Second Edition), Chapter 23, Problem 23.1P , additional homework tip  22

From the Table 23-1, the product is a mixture of o+p isomer more than 95%.

The mechanism for the given reaction is given below.

Since the given reaction is an example of electrophilic aromatic substitution reaction, the first step is the formation of the electrophile as given below.

Initially, electron-rich chlorine of the ethyl chloride is coordinated with an electron-deficient aluminum of AlCl3, followed by heterolysis of C-Cl bond to form the corresponding acylium cation, which is nothing but the required electrophile.

Organic Chemistry: Principles and Mechanisms (Second Edition), Chapter 23, Problem 23.1P , additional homework tip  23

The formed electrophile, acylium cation, then undergoes electrophilic addition to the benzene ring, followed by electrophilic elimination mechanism, to form the ortho and para isomers shown below:

For ortho isomer:

Organic Chemistry: Principles and Mechanisms (Second Edition), Chapter 23, Problem 23.1P , additional homework tip  24

For para isomer:

Organic Chemistry: Principles and Mechanisms (Second Edition), Chapter 23, Problem 23.1P , additional homework tip  25

Conclusion

The major product for the given reaction is predicted, and the complete, detailed mechanism for the same reaction is drawn on the basis of the electrophilic aromatic substitution reaction.

Interpretation Introduction

(d)

Interpretation:

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

Concept introduction:

In the case of an electrophilic aromatic substitution reaction, a substituent influences the site of reaction. The electron-donating groups are ortho/para directing groups while electron-withdrawing groups are meta directing groups in the electrophilic aromatic substitution reaction. The Friedel-Crafts alkylation and acylation are an example of an electrophilic aromatic substitution reaction. The chlorination of the aromatic ring can be carried out by reacting with Cl2 in the presence of FeCl3, which is also an example of an electrophilic aromatic substitution reaction. In Friedel-Crafts reaction, the first step is the formation of an electrophile, and then the electrophilic addition-elimination takes place with the aromatic ring and the electrophile.

Expert Solution
Check Mark

Answer to Problem 23.1P

The major product for the given reaction is

Organic Chemistry: Principles and Mechanisms (Second Edition), Chapter 23, Problem 23.1P , additional homework tip  26

The complete, detailed mechanism for the given reaction is given below.

Formation of the electrophile:

Organic Chemistry: Principles and Mechanisms (Second Edition), Chapter 23, Problem 23.1P , additional homework tip  27

Formation of the product:

Organic Chemistry: Principles and Mechanisms (Second Edition), Chapter 23, Problem 23.1P , additional homework tip  28

Explanation of Solution

The given reaction is

Organic Chemistry: Principles and Mechanisms (Second Edition), Chapter 23, Problem 23.1P , additional homework tip  29

It is noticed that the given substrate is treated with Br2 in the presence of FeBr3; it is an example of an electrophilic aromatic substitution reaction. Since the acyl group is a meta director, the major product of the given reaction is m-bromoacetophenone.

Organic Chemistry: Principles and Mechanisms (Second Edition), Chapter 23, Problem 23.1P , additional homework tip  30

The mechanism for the given reaction is given below.

Since the given reaction is an example of an electrophilic aromatic substitution reaction, the first step is the formation of the electrophile as given below.

Initially, one of the electron-rich bromine atoms of Br2 is coordinated with an electron-deficient iron metal of FeBr3 followed by heterolysis of Br-Br bond, to form the corresponding cation, which is nothing but the required electrophile.

Organic Chemistry: Principles and Mechanisms (Second Edition), Chapter 23, Problem 23.1P , additional homework tip  31

The formed electrophile (Br+) then undergoes electrophilic addition to the benzene ring, followed by electrophilic elimination mechanism, to form the major meta isomer as the product, as shown below:

Organic Chemistry: Principles and Mechanisms (Second Edition), Chapter 23, Problem 23.1P , additional homework tip  32

Conclusion

The major product for the given reaction is predicted, and the complete, detailed mechanism for the same reaction is drawn on the basis of the electrophilic aromatic substitution reaction.

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Chapter 23 Solutions

Organic Chemistry: Principles and Mechanisms (Second Edition)

Ch. 23 - Prob. 23.11PCh. 23 - Prob. 23.12PCh. 23 - Prob. 23.13PCh. 23 - Prob. 23.14PCh. 23 - Prob. 23.15PCh. 23 - Prob. 23.16PCh. 23 - Prob. 23.17PCh. 23 - Prob. 23.18PCh. 23 - Prob. 23.19PCh. 23 - Prob. 23.20PCh. 23 - Prob. 23.21PCh. 23 - Prob. 23.22PCh. 23 - Prob. 23.23PCh. 23 - Prob. 23.24PCh. 23 - Prob. 23.25PCh. 23 - Prob. 23.26PCh. 23 - Prob. 23.27PCh. 23 - Prob. 23.28PCh. 23 - Prob. 23.29PCh. 23 - Prob. 23.30PCh. 23 - Prob. 23.31PCh. 23 - Prob. 23.32PCh. 23 - Prob. 23.33PCh. 23 - Prob. 23.34PCh. 23 - Prob. 23.35PCh. 23 - Prob. 23.36PCh. 23 - Prob. 23.37PCh. 23 - Prob. 23.38PCh. 23 - Prob. 23.39PCh. 23 - Prob. 23.40PCh. 23 - Prob. 23.41PCh. 23 - Prob. 23.42PCh. 23 - Prob. 23.43PCh. 23 - Prob. 23.44PCh. 23 - Prob. 23.45PCh. 23 - Prob. 23.46PCh. 23 - Prob. 23.47PCh. 23 - Prob. 23.48PCh. 23 - Prob. 23.49PCh. 23 - Prob. 23.50PCh. 23 - Prob. 23.51PCh. 23 - Prob. 23.52PCh. 23 - Prob. 23.53PCh. 23 - Prob. 23.54PCh. 23 - Prob. 23.55PCh. 23 - Prob. 23.56PCh. 23 - Prob. 23.57PCh. 23 - Prob. 23.58PCh. 23 - Prob. 23.59PCh. 23 - Prob. 23.60PCh. 23 - Prob. 23.61PCh. 23 - Prob. 23.62PCh. 23 - Prob. 23.63PCh. 23 - Prob. 23.64PCh. 23 - Prob. 23.65PCh. 23 - Prob. 23.66PCh. 23 - Prob. 23.67PCh. 23 - Prob. 23.68PCh. 23 - Prob. 23.69PCh. 23 - Prob. 23.70PCh. 23 - Prob. 23.71PCh. 23 - Prob. 23.72PCh. 23 - Prob. 23.73PCh. 23 - Prob. 23.74PCh. 23 - Prob. 23.75PCh. 23 - Prob. 23.76PCh. 23 - Prob. 23.77PCh. 23 - Prob. 23.78PCh. 23 - Prob. 23.79PCh. 23 - Prob. 23.80PCh. 23 - Prob. 23.81PCh. 23 - Prob. 23.82PCh. 23 - Prob. 23.83PCh. 23 - Prob. 23.84PCh. 23 - Prob. 23.85PCh. 23 - Prob. 23.86PCh. 23 - Prob. 23.87PCh. 23 - Prob. 23.88PCh. 23 - Prob. 23.89PCh. 23 - Prob. 23.90PCh. 23 - Prob. 23.91PCh. 23 - Prob. 23.92PCh. 23 - Prob. 23.93PCh. 23 - Prob. 23.94PCh. 23 - Prob. 23.95PCh. 23 - Prob. 23.96PCh. 23 - Prob. 23.97PCh. 23 - Prob. 23.1YTCh. 23 - Prob. 23.2YTCh. 23 - Prob. 23.3YTCh. 23 - Prob. 23.4YTCh. 23 - Prob. 23.5YTCh. 23 - Prob. 23.6YTCh. 23 - Prob. 23.7YTCh. 23 - Prob. 23.8YTCh. 23 - Prob. 23.9YTCh. 23 - Prob. 23.10YTCh. 23 - Prob. 23.11YTCh. 23 - Prob. 23.12YTCh. 23 - Prob. 23.13YTCh. 23 - Prob. 23.14YT
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