CHAPTER 22REACTIONS OF BENZENE AND ITS DERIVATIVES

MULTIPLE CHOICE
1. What is the major organic product obtained from the following reaction?

a.
b.
c.
d.

1
2
3
4

ANS: B
2. What is the major organic product obtained from the following reaction?

a.
b.
c.
d.

1
2
3
4

ANS: B
3. What is the major organic product obtained from the following reaction?

a.
b.
c.
d.

1
2
3
4

ANS: D
4. What is the major organic product obtained from the following reaction?

a.
b.
c.
d.

1
2
3
4

ANS: B
5. What is the major organic product obtained from the following reaction?

a.
b.
c.
d.

1
2
3
4

ANS: B

6. What is the electrophile in the reaction of benzene with a mixture of nitric acid and sulfuric acid?
a. HONO
b. NO+
c. NO2+
d. benzene
ANS: B
7. What is the electrophile in the reaction of benzene with acetyl chloride, CH 3COCl, and AlCl3?
a. CH3CO+
b. CH3+
c. CH3CO2
d. benzene
ANS: A
8. What is the electrophile in the reaction of benzene with tert-butyl chloride and AlCl3?
a. CH3+
b. Cl+
c. (CH3)C+
d. benzene
ANS: C
9. What is the role of AlCl3 in Friedel Crafts acylations using acid chlorides?
a. Lewis acid
b. electrophile
c. base
d. nucleophile
ANS: A
10. What is the role of FeBr3 in electrophilic aromatic bromination of benzene using Br 2?
a. nucleophile
b. electrophile
c. Lewis acid
d. base
ANS: C
11. Which of the following undergoes the most rapid nitration upon treatment with HNO 3/H2SO4?
a. toluene
b. benzene
c. bromobenzene
d. nitrobenzene
ANS: A
12. Which of the following undergoes the most rapid bromination upon treatment with Br 2/FeBr3?
a. benzene
b. nitrobenzene
c. bromobenzene
d. anisole
ANS: D

13. Which of the following undergoes the most rapid sulfonation upon treatment with fuming sulfuric
acid?
a. benzene
b. benzoic acid
c. benzonitrile
d. nitrobenzene
ANS: A
14. Which of the following undergoes the most rapid acylation upon treatment with acetyl chloride and
AlCl3?
a. benzene
b. toluene
c. chlorobenzene
d. 1,4-dichlorobenzene
ANS: B
15. Which of the following sets of substituents are all ortho/para directing in electrophilic aromatic
substitution reactions?
a. Cl, CH3, CN
b. Br, OH, COCH3
c. Cl, OH, CH3
d. CN, NO2, COCH3
ANS: C
16. Which of the following sets of substituents are all ortho/para directing in electrophilic aromatic
substitution reactions?
a. Br, CH3, NO2
b. CH3, NH2, Br
c. Cl, OCH3, COCH3
d. NO2, COCH3, COOH
ANS: B
17. Which of the following sets of substituents are all meta directing in electrophilic aromatic substitution
reactions?
a. CN, NO2, COCH3
b. CH3, OCH3, COCH3
c. Cl, NH2, CH3
d. CH3, NH3, OCH3
ANS: A
18. Which of the following sets of substituents are all meta directing in electrophilic aromatic substitution
reactions?
a. CH3, OH, Br
b. Cl, NH2, CN
c. COCH3, NO2, COOH
d. NH2, COCH3, OH
ANS: C

19. Which of the following sets of substituents are all activating groups in electrophilic aromatic
substitution reactions?
a. CH3, OCH3, COCH3
b. Cl, CN, NO2
c. Cl, NH2, CH3
d. CH3, NH2, OCH3
ANS: D
20. Which of the following sets of substituents are all activating groups in electrophilic aromatic
substitution reactions?
a. Br, NH2, CH3
b. CH3, NH2, OCH3
c. OH, COCH3, CH3,
d. Br, CN, NO2
ANS: B
21. Which of the following sets of substituents are all deactivating groups in electrophilic aromatic
substitution reactions?
a. Cl, CN, NO2
b. Cl, NH2, CH3
c. CH3, OCH3, COCH3
d. CH3, NH2, OCH3
ANS: A
22. Which of the following sets of substituents are all deactivating groups in electrophilic aromatic
substitution reactions?
a. Cl, OH, CH2CH3
b. CH3, Br, COCH3
c. CH3, NH2, OH
d. COCH3, NO2, Br
ANS: D
23. Which of the following substituents is ortho/para directing and deactivating in electrophilic aromatic
substitution reactions?
a. OH
b. Cl
c. CH3
d. NO2
ANS: B
24. Which of the following substituents is ortho/para directing and deactivating in electrophilic aromatic
substitution reactions?
a. COCH3
b. NH3
c. Br
d. CH2CH3
ANS: C

25. Which of the following reactions or reaction sequences will not give isopropylbenzene as the major
product?
a. treatment of benzene with isopropyl alcohol and HF
b. treatment of benzene with 1-chloropropane and AlCl 3
c. treatment of benzene with propanoyl chloride and AlCl3; followed by reaction with
Zn(Hg) and HCl
d. treatment of benzene with 1-propene and HF
ANS: C
26. Which of the following reactions or sequences will provide 1-propylbenzene as the major product?
a. treatment of benzene with isopropyl alcohol and HF
b. treatment of benzene with propanoyl chloride and AlCl3; followed by reaction with
Zn(Hg) and HCl
c. treatment of benzene with 1-chloropropane and AlCl 3
d. treatment of benzene with 1-propene and HF
ANS: B
27. Which of the following are valid resonance structures of the electophile involved in Friedel-Crafts
acylation of benzene upon treatment with CH3COCl and AlCl3?

a.
b.
c.
d.

1
2
3
4

ANS: A
28. Which of the following is the structure of the complex of Br 2 with FeBr3 involved in the electrophilic
bromination of benzene?

a.
b.
c.
d.

1
2
3
4

ANS: D

29. Which of the following sets of reagents does not result in alkylation of benzene?
a. tert-butyl chloride + AlCl3
b. tert-butyl alcohol + H3PO4
c. methylpropene + HF
d. methylpropane + H2SO4
ANS: D
30. Why does nitrobenzene fail to undergo Fieldel-Crafts alkylation with tert-butyl chloride and AlCl3?
a. nitrobenzene reacts with AlCl3
b. nitrobenzene is a poor nucleophile
c. the nitro group is a strong electron donating group
d. the tert-butyl cation is a poor electrophile
ANS: B
31. Why does anisole undergo bromination with Br2 in the absence of FeBr3 whereas bromination of
benzene requires the presence of FeBr 3?
a. anisole is a better nucleophile than benzene
b. the methoxy group of anisole is an inductive electron withdrawing substituent
c. Br2 is a good nucleophile
d. the reaction is accelerated by light
ANS: A
32. What is the major organic product obtained from the following reaction?

a.
b.
c.
d.

1
2
3
4

ANS: B

33. What is the major organic product obtained from the following reaction?

a.
b.
c.
d.

1
2
3
4

ANS: C
34. What is the major organic product obtained from the following reaction?

a.
b.
c.
d.

1
2
3
4

ANS: A
35. What is the major organic product obtained from the following reaction?

a.
b.
c.
d.

1
2
3
4

ANS: B
36. What is the major organic product obtained from the following reaction?

a.
b.
c.
d.

1
2
3
4

ANS: B
37. What is the major organic product obtained from the following reaction?

a.
b.
c.
d.

1
2
3
4

ANS: D

38. What is the major organic product obtained from the following reaction?

a.
b.
c.
d.

1
2
3
4

ANS: D
39. What is the major organic product obtained from the following reaction?

a.
b.
c.
d.

1
2
3
4

ANS: D

10

40. What is the major organic product obtained from the following reaction?

a.
b.
c.
d.

1
2
3
4

ANS: B
41. What is the major organic product obtained from the following reaction?

a.
b.
c.
d.

1
2
3
4

ANS: D

11

42. What is the major organic product obtained from the following sequence of reactions?

a.
b.
c.
d.

1
2
3
4

ANS: A
43. What is the major organic product obtained from the following sequence of reactions?

a.
b.
c.
d.

1
2
3
4

ANS: C

12

44. What is the major organic product obtained from the following sequence of reactions?

a.
b.
c.
d.

1
2
3
4

ANS: A
45. What is the major organic product obtained from the following sequence of reactions?

a.
b.
c.
d.

1
2
3
4

ANS: C

13

46. What is the major organic product obtained from the following sequence of reactions?

a.
b.
c.
d.

1
2
3
4

ANS: D
47. What is the major organic product obtained from the following sequence of reactions?

a.
b.
c.
d.

1
2
3
4

ANS: A

14

48. Which of the following cannot be prepared from benzene in two synthetic steps?

a.
b.
c.
d.

1
2
3
4

ANS: D
49. Which of the following cannot be prepared from benzene in two synthetic steps?

a.
b.
c.
d.

1
2
3
4

ANS: A

15

50. Which of the following is the reactive intermediate in the nucleophilic substitution of 4-bromo-1nitrobenzene with sodium hydroxide?

a.
b.
c.
d.

1
2
3
4

ANS: A
51. Which of the following is the reactive intermediate in the nucleophilic substitution of 4-bromo-1toluene with sodium amide?

a.
b.
c.
d.

1
2
3
4

ANS: D

16

52. Which of the following is the reactive intermediate formed in the electrophilic bromination of toluene
with Br2, FeBr3?

a.
b.
c.
d.

1
2
3
4

ANS: C
53. Which of the following is the reactive intermediate formed in the electrophilic nitration of
nitrobenzene with HNO3 and H2SO4?

a.
b.
c.
d.

1
2
3
4

ANS: B

17

54. Which of the following is the reactive intermediate formed in the electrophilic Friedel-Crafts acylation
of toluene with CH3COCl and AlCl3?

a.
b.
c.
d.

1
2
3
4

ANS: D
55. Which of the following compounds undergoes the most rapid nucleophilic substitution with hydroxide
ion?

a.
b.
c.
d.

1
2
3
4

ANS: D

18

56. Which of the following compounds undergoes the most rapid nucleophilic substitution with hydroxide
ion?

a.
b.
c.
d.

1
2
3
4

ANS: C
57. Which of the following chlorobenzenes produces a single isomer upon treatment with NaNH 2?

a.
b.
c.
d.

1
2
3
4

ANS: D
58. Which of the following chlorobenzenes does not undergo nucleophilic aromatic substitution upon
treatment with NaNH2?

19

a.
b.
c.
d.

1
2
3
4

ANS: A
59. Which mechanism accounts for the reaction of 4-bromo-1-nitrobenzene with sodium hydroxide to
form 4-nitrophenol?
a. Bimolecular nucleophilic substitution (SN2)
b. Nucleophilic aromatic substitution by elimination-addition
c. Nucleophilic aromatic substitution by addition-elimination
d. Electrophilic aromatic substitution
ANS: C
60. Which mechanism accounts for the reaction of chlorobenzene with acetyl chloride and AlCl 3 to form
4-chloroacetophenone?
a. Bimolecular nucleophilic substitution (SN2)
b. Nucleophilic aromatic substitution by elimination-addition
c. Nucleophilic aromatic substitution by addition-elimination
d. Electrophilic aromatic substitution
ANS: D
61. Which mechanism accounts for the reaction of benzyl chloride with sodium cyanide to form
cyanomethylbenzene (phenylacetonitrile, PhCH2CN)?
a. Bimolecular nucleophilic substitution (SN2)
b. Nucleophilic aromatic substitution by elimination-addition
c. Nucleophilic aromatic substitution by addition-elimination
d. Electrophilic aromatic substitution
ANS: A
62. Which mechanism accounts for the reaction of 4-bromotoluene with sodium amide to form a mixture
of 3- and 4-aminotoluene?
a. Bimolecular nucleophilic substitution (SN2)
b. Nucleophilic aromatic substitution by elimination-addition
c. Nucleophilic aromatic substitution by addition-elimination
d. Electrophilic aromatic substitution
ANS: B
63. What type of intermediate is formed in the reaction between chlorobenzene and tert-butyl chloride and
AlCl3 to give 4-chloro-1-tert-butylbenzene?
a. Meisenheimer complex
b. benzyne
c. cyclohexadienyl cation
d. benzyl radical
ANS: C

20

64. What type of intermediate is formed in the reaction between bromobenzene and sodium amide to give
aniline?
a. Meisenheimer complex
b. benzyne
c. cyclohexadienyl cation
d. benzyl radical
ANS: B
65. What type of intermediate is formed in upon irradiation of a mixture of toluene and chlorine to give
benzyl chloride?
a. Meisenheimer complex
b. benzyne
c. cyclohexadienyl cation
d. benzyl radical
ANS: D
68. Which of the following is not true about benzynes?
a. They are planar
b. They are formed upon dehydrohalogenation of aryl halides
c. They are aromatic
d. They are intermediates in nucleophilic aromatic substitution reaction which take place by
an addition-elimination mechanism
ANS: D

21

69. Predict the product of the following reaction:

E

A)
E

B)
E

C)
E

D)
E

E)

none of these
ANS: A

22

70 What major product would you expect from the following reaction?
OH
HNO3
H2SO4

A)
OH

NO2

B)
OH

O2N

C)
OH NO2

D)
OH

NO2

E)
OH

NO2
A

ANS: A

23

71. Predict the major organic product of the following reaction.

O
NO2
CH3O
NO2
A)

O
Br

NO2

CH3O
NO2
B)

Br

O
NO2

CH3O
NO2
C)

Br
NO2

CH3O
NO2
D)

Br

OH

NO2

CH3O
NO2

E)

24

Br 2 / FeBr 3

O
NO2
Br

CH3O
NO2
ANS: A

PROBLEM
1. What is the major organic product obtained from the following reaction?

ANS:

2. What is the major organic product obtained from the following reaction?

ANS:

25

3. What is the major organic product obtained from the following reaction?

ANS:

4. What is the major organic product obtained from the following reaction?

ANS:

5. What is the major organic product obtained from the following reaction?

26

ANS:

27

6. What is the major organic product obtained from the following reaction?

ANS:

7. What is the major organic product obtained from the following sequence of reactions (if a reaction is
likely to give you a mixture of ortho and para disubstituted compounds you should assume that they
can be separated; continue the synthesis with either one)?

ANS:

8. What is the major organic product obtained from the following reaction (if a reaction is likely to give
you a mixture of ortho and para disubstituted compounds you should assume that they can be
separated; continue the synthesis with either one)?

28

29

ANS:

9. What is the major organic product obtained from the following sequence of reactions (if a reaction is
likely to give you a mixture of ortho and para disubstituted compounds you should assume that they
can be separated; continue the synthesis with either one)?

ANS:

10. What is the major organic product obtained from the following reaction (assume that mixtures of ortho
and para disubstituted compounds can be separated; continue the synthesis with either one)?

ANS:

or ortho isomer

30

11. What is the major organic product obtained from the following reaction (assume that mixtures of ortho
and para disubstituted compounds can be separated; continue the synthesis with either one)?

ANS:

12. Provide the structure (a single resonance contributor) of the key intermediate in the electrophilic
aromatic nitration of chlorobenzene.

ANS:

13. Provide the structure (a single resonance contributor) of the key intermediate in the electrophilic
aromatic chlorinatio of nitroobenzene.

31

ANS:

14. Provide the structure (a single resonance contributor) of the key intermediate in the following reaction.

ANS:

15. Provide the structure (a single resonance contributor) of the key intermediate in the following reaction
.

ANS:

16) Provide a series of synthetic steps by which 2-bromo-4-nitrobenzoic acid can be prepared
32

from toluene.
Answer:
1. HNO3, H2SO4
2. Br2, FeBr3
3. KMnO4, OH-,
4. H+
Diff: 3
17) Provide a series of synthetic steps by which 3-bromoethylbenzene can be prepared from
benzene.
Answer:
1. CH3COCl, AlCl3
2. Br2, FeBr3
3. Zn(Hg), HCl
Diff: 3
18) Provide a series of synthetic steps by which 4-t-butylbenzoic acid can be prepared from
toluene.
Answer: 1. (CH3)3CCl, AlCl3
2. KMnO4, OH-,
3. H+
Diff: 3
19) Provide a series of synthetic steps by which p-nitrobutylbenzene can be prepared from
benzene.
Answer:
1. CH3CH2CH2COCl, AlCl3
2. Zn(Hg), HCl
3. HNO3, H2SO4
Diff: 3
20) Provide a series of synthetic steps by which 4-phenylheptan-4-ol can be prepared from
benzene.
Answer:
1. Br2, FeBr3
2. Mg, ether
3. CH3CH2CH2COCH2CH2CH3
4. H3O+
Diff: 3

33