TB Chapter16

Chapter 16 – Chemistry of Benzene:
Electrophilic Aromatic Substitution
MATCH a structure or term from the following list with each description below. Place the letter of the structure
or term in the blank to the left of the description.
a. benzyne
b.
c.
d. electron-donating
e.
f. Meisenheimer complex
g.
h. electron-withdrawing
1. The reactive electrophile in Friedel-Crafts acylation reactions.
Answer: g
2. The electrophile in aromatic nitration.
Answer: b
3. Groups which activate aromatic rings towards electrophilic substitution.
Answer: d
4. Groups which activate aromatic rings towards nucleophilic substitution.
Answer: h
5. Intermediate in the elimination-addition mechanism of nucleophilic aromatic substitution.
Answer: a
Consider the Friedel-Crafts alkylation reaction below to answer the following questions:
6. Draw the structure of the electrophilic intermediate in this reaction.
Answer:
7. What is the role of the AlCl3 in the reaction?
Answer: The AlCl3 is a Lewis acid catalyst that assists in the ionization of the alkyl halide to give the
carbocation electrophile.
Test Items for McMurry’s Organic Chemistry, Seventh Edition 145

8. Write the complete stepwise mechanism for this reaction. Show all electron flow with arrows and include
all intermediate structures.
Answer:
+ -
CH3CH2--Cl + AlCl3 CH3CH2 + Cl -AlCl3
CH2CH3
+ - CH2CH3
CH3CH2 H Cl -AlCl3 + HCl + AlCl3
H
9. Aniline reacts with nitrous acid, , to yield a stable diazonium salt. This diazonium salt undergoes
electrophilic aromatic substitution on activated aromatic rings to yield brightly colored azo compounds that
are widely used as dyes. The intermediate structures for the mechanism of this reaction are given below.
Show all electron flow with arrows for this mechanism on the structures provided.
Answer:
146 Chapter 16: Chemistry of Benzene: Electrophilic Aromatic Substitution

Consider the data below to answer the following questions.
The -NH2 group is listed in our textbook as the strongest o,p-directing activator in electrophilic aromatic
substitution reactions. However, when aniline is subjected to standard nitration conditions poor yields of
m-nitroaniline result.
10. Draw all the resonance forms of aniline showing the electron-donating effect of the -NH 2 substituent.
Answer:
11. Clearly, the reaction conditions are influencing the directing effect of the -NH 2 group. Explain why this
occurs, using both words and structures.
Answer:
+
NH2 NH3
H2SO4 +
+ NO2
HNO3
+ + +
NH3 NH3 NH3
+ +
H O2N +
NO2 H
H NO2
ortho attack para attack meta attack
When aniline is placed in strong acid the nitrogen atom is protonated. Electrophilic aromatic
substitution on the anilinium ion—whose aromatic ring is now deactivated by a positively
charged substituent—occurs primarily at the meta position since this keeps the positive charge
of the intermediate carbocation away from the positively charged nitrogen. The intermediates
shown above for ortho and para substitution are destabilized more than the intermediate for
meta substitution, so m-nitroaniline is the major product.

Consider the reaction below to answer the following questions.
12. Write the complete stepwise mechanism for the formation of the ortho product. Show all intermediate
structures and show all electron flow with arrows.
Answer:
13. Draw resonance structures for the intermediate carbocation that explain the directing effect of the -Br.
Answer:
Rank the compounds in each group below according to their reactivity toward electrophilic aromatic
substitution (most reactive ; least reactive ). Place the number corresponding to the compounds’
relative reactivity in the blank below the compound.
14.
Answer:

15.
Answer:
16. At what position, and on what ring, is bromination of phenyl benzoate expected to occur? Explain your
answer.
Answer:
Attack occurs in the activated ring and yields ortho and para bromination

To answer the following questions, refer to the data below:
Isobutylbenzene is the starting material for the industrial synthesis of the NSAID, ibuprofen.
17. Attempts to prepare isobutylbenzene by direct Friedel-Crafts alkylation of benzene result in tert-
butylbenzene as the major product. Write the complete stepwise mechanism for this reaction, showing all
electron flow with arrows and showing all intermediate structures.
Answer:
H -
AlCl4 +
Cl AlCl3 +
+
+ -
H Cl -AlCl3 + HCl + AlCl3
H
18. Propose a synthesis for isobutylbenzene which avoids the problems of direct Friedel-Crafts alkylation.
Answer:
19. Would you expect (nitromethyl)benzene to be more reactive or less reactive than toluene toward
electrophilic substitution? Explain.
Answer: (Nitromethyl)benzene should be less reactive than toluene owing to the strong inductive
electron withdrawing effect of the nitro group.

Consider the reaction below to answer the following questions.
20. The nucleophile in the reaction is:
Answer: A
21. The Lewis acid catalyst in the reaction is:
Answer: C
22. This reaction proceeds _____________(faster or slower) than benzene.
Answer: slower
23. Draw the structure of product D.
Answer:
24. The following reaction proceeds by an intramolecular nucleophilic aromatic substitution mechanism. Write
the complete stepwise mechanism, showing all intermediate structures and all electron flow with arrows.
Answer:

25. Tetracyclone is often used to trap benzynes as Diels-Alder adducts. What is the structure of the Diels-
Alder adduct that results when benzyne is trapped by tetracyclone?
Answer:
26. On the structural intermediates below, show all electron flow with arrows for the nucleophilic aromatic
subsitution reaction of p-nitrochlorobenzene with KOH.
Answer:

Given the major organic product(s) of each of the following reactions. If none is predicted, write “N.R.”
27.
Answer:
28.
1) NaOH
H3C Cl
2) H3O+
Answer: NR. Nucleophilic Aromatic Substitution requires an electron-withdrawing group in the ortho or
para position. A methyl group is electron donating, and substitution will not occur.
29.
Answer:

30.
Answer:
31.
Answer:
32.
Answer:

33.
Answer:
34.
Answer:
35.
Answer:
36.
Answer:

37.
Answer:
38.
Answer:
39.
Answer:
(Friedel-Crafts reactions do not proceed in the presence of a deactivating group)
40.

Answer:
41.
Answer:
42.
Answer:

Choose the best reagent(s) from the list provided below for carrying out the following conversions. Place the
letter of the reagent in the box beside the reaction number over the arrow. There is only one answer for each
reaction.
a.
b.
c.
d.
e.
f. ClCO(CH2)2CH3, AlCl3
g. CH3CH2CH2CH2Cl, AlCl3
h.
i. NBS, peroxides
43.
Answer:
44.
Answer:

45.
Answer:
46.
Answer:
Propose syntheses to carry out each of the following conversions. Assume ortho and para isomers can be
separated.
47.

Answer:
48.
CH3 NH2
(H3C)3C C(CH3)3
CH3
Answer:
CH3 NO2 NH2 NH2
HNO3 1)Fe, H3O+ ClC(CH3)3 (H3C)3C C(CH3)3

H2SO4 2) HO- AlCl3
CH3 CH3 CH3
49.
Answer:

50.
CO2H
Cl
Cl
Answer:
CH3 CH3 CO2H
ClCH3 Cl2 Cl KMnO4 Cl

AlCl3 FeCl3 H3O+
Cl Cl
51.
Answer:
52.

Answer:
Propose syntheses of the following compounds starting with benzene or toluene. Assume ortho and para
isomers can be separated.
53.
Answer:
54.
Answer:

TB Chapter16

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Chapter 16 – Chemistry of Benzene:

Electrophilic Aromatic Substitution

1. The reactive electrophile in Friedel-Crafts acylation reactions.

2. The electrophile in aromatic nitration.

3. Groups which activate aromatic rings towards electrophilic substitution.

4. Groups which activate aromatic rings towards nucleophilic substitution.

5. Intermediate in the elimination-addition mechanism of nucleophilic aromatic substitution.

6. Draw the structure of the electrophilic intermediate in this reaction.

7. What is the role of the AlCl3 in the reaction?

Test Items for McMurry’s Organic Chemistry, Seventh Edition 145

146 Chapter 16: Chemistry of Benzene: Electrophilic Aromatic Substitution

Test Items for McMurry’s Organic Chemistry, Seventh Edition 147

148 Chapter 16: Chemistry of Benzene: Electrophilic Aromatic Substitution

Test Items for McMurry’s Organic Chemistry, Seventh Edition 149

150 Chapter 16: Chemistry of Benzene: Electrophilic Aromatic Substitution

20. The nucleophile in the reaction is:

21. The Lewis acid catalyst in the reaction is:

22. This reaction proceeds _____________(faster or slower) than benzene.

23. Draw the structure of product D.

Test Items for McMurry’s Organic Chemistry, Seventh Edition 151

152 Chapter 16: Chemistry of Benzene: Electrophilic Aromatic Substitution

Test Items for McMurry’s Organic Chemistry, Seventh Edition 153

154 Chapter 16: Chemistry of Benzene: Electrophilic Aromatic Substitution

Test Items for McMurry’s Organic Chemistry, Seventh Edition 155

(Friedel-Crafts reactions do not proceed in the presence of a deactivating group)

156 Chapter 16: Chemistry of Benzene: Electrophilic Aromatic Substitution

Test Items for McMurry’s Organic Chemistry, Seventh Edition 157

158 Chapter 16: Chemistry of Benzene: Electrophilic Aromatic Substitution

Test Items for McMurry’s Organic Chemistry, Seventh Edition 159

CH3 NO2 NH2 NH2

HNO3 1)Fe, H3O+ ClC(CH3)3 (H3C)3C C(CH3)3

CH3 CH3 CH3

160 Chapter 16: Chemistry of Benzene: Electrophilic Aromatic Substitution

ClCH3 Cl2 Cl KMnO4 Cl

Test Items for McMurry’s Organic Chemistry, Seventh Edition 161

162 Chapter 16: Chemistry of Benzene: Electrophilic Aromatic Substitution

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