ch15 Organic Chemistry

Chapter Fifteen
MULTIPLE CHOICE QUESTIONS

Topic: Mechanisms and Intermediates
Section: 15.2
Difficulty Level: Medium
1. Which of these is the rate-determining step in the nitration of benzene?
A) Protonation of nitric acid by sulfuric acid
B) Protonation of sulfuric acid by nitric acid
C) Loss of a water molecule by the protonated species to produce the nitronium ion
D) Addition of the nitronium to benzene to produce the arenium ion
E)
Loss of a proton by the arenium ion to form nitrobenzene
Ans: D
Topic: Other EAS Considerations
Section: 15.2
2. In electrophilic aromatic substitution, the attacking species (the electrophile) necessarily
is a:
A) neutral species.
B) positively charged species.
C) lewis acid.
D) proton.
E)
carbocation.
Ans: C
Section: 15.3
Difficulty Level: Easy
3. The electrophilic bromination or chlorination of benzene requires, in addition to the
halogen:
A) a hydroxide ion.
B) a Lewis base.
C) a Lewis acid.
D) peroxide.
E)
ultraviolet light.
Ans: C
45
Topic: Synthesis
Section: 15.3
4. Consider the following reaction: what is the expected product?
NH2
Br2, H2O
Cl
Br
Br
H2N
Cl
Br
NH2
Cl
Br
Cl
NH2
II
NH2
Br
Br
Br
III
Br
NH2
Br
A)
B)
C)
D)
E)
Ans:
I
II
III
IV
V
B
Cl
Cl
IV
Topic: Functional Group Tests

Sections: 14.2 ,14.3 and 15.3
5. Which reagent would you use as the basis for a simple chemical test that would
distinguish between toluene and vinylbenzene (C6H5CH=CH2)?
A) NaOH/H2O
B) Br2/CCl4
C) NaBH4
D) HCl/H2O
E)
NaI in acetone
Ans: B
46
Topic: Nomenclature, Functional Group Tests

Section: 14.2 , 14.11 and 15.3
6. Which reagent or test could you use to distinguish between phenylacetylene and
vinylbenzene?
A) NaOH/H2O
B) Br2/CCl4
C) IR Spectroscopy
D) CrO3/H2SO4
E)
Concd. H2SO4
Ans: C
Topic: Synthesis
Section: 15.6
7. Which of the following reactions could be used to synthesize tert-butylbenzene?
H 2S O 4
A)
C 6H 6 + C H 2= C (C H 3)2
H 2S O 4
B)
C 6H 6 + (C H 3)3C O H
A lC l3
C)
C 6H 6 + (C H 3)3C C l
D) All of the above
E)
None of the above
Ans: D
47
Topic: Synthesis
Section: 15.6
8. Which of the following reactions would yield isopropylbenzene as the major product?
C H 3C H C H 2
A)
B enzene
H 2S O 4
C
H
3C H C H 3
B)
B enzene
H 2S O
C H 3C H C H
C)
B enzene
D)
O H
B enzene
C l
A lC l3
C H 3C H 2C H 2C l
A lC l3
E)
All of these
Ans: E
Topic: Synthesis
Section: 15.6
9. Which of the following reactions would produce isopropylbenzene?
Cl
A)
Benzene
AlCl3
B)
Benzene
HF
OH
C)
Benzene
H2SO4
Br
D)
Benzene
AlCl3
E)
All of these
Ans: E
48
Topic: Synthesis
Section: 15.6
Difficulty Level: Hard
10. Which of the following reactions would produce cumene?
Cl
A)
Benzene
AlCl3
B)
Benzene
HF
OH
C)
Benzene
H2SO4
Br
D)
Benzene
AlCl3
E)
All of these
Ans: E
Topic: Synthesis
Section: 15.6
11. Which of the following reactions would yield cumene as the major product?
C H 3C H C H 2
A)
B enzene
H 2S O 4
C
H
3C H C H 3
B)
B enzene
H 2S O
C H 3C H C H
C)
B enzene
D)
O H
B enzene
C l
A lC l3
C H 3C H 2C H 2C l
A lC l3
E)
All of these
Ans: E
49
Topic: Synthesis
Sections: 11.9 and 15.6
12. Which of these is a satisfactory synthesis of 1-chloro-2-phenylethane?
A) C6H5CH2CH3 + Cl2, Fe
B) C6H5CH2CH3 + Cl2, 400C
C) C6H5CH2CH2OH + SOCl2
D) C6H5CH=CH2 + HCl, peroxide
E)
C6H6 + CH3CH2Cl, AlCl3
Ans: C
Topic: Synthesis
Sections: 11.9 and 15.6
13. Which of these is a satisfactory synthesis of 1-chloro-2-phenylethane?
A) C6H5CH2CH3 + Cl2, Fe
B) C6H5CH2CH3 + Cl2, 400C
C) C6H5CH2CH2OH + PCl5
D) C6H5CH=CH2 + HCl, peroxide
E)
C6H6 + CH3CH2Cl, AlCl3
Ans: C
Topic: Nomenclature, Reaction Products
Section: 14.2 and 15.6
14. What is the chief product of the Friedel-Crafts alkylation of benzene with 1-butene and
HF?
A) butylbenzene
B) 2-phenylbutane
C) 2-methyl-1-phenylpropane
D) t-butylbenzene
E)
2,2-diphenylbutane
Ans: B
50

15. What is the chief product of the Friedel-Crafts alkylation of benzene with 1-butene and
AlCl3?
A) butylbenzene
B) 2-phenylbutane
C) 2-methyl-1-phenylpropane
D) t-butylbenzene
E)
2,2-diphenylbutane
Ans: B
Section: 15.8
16. Which of these liquids would be unsuitable as an inert solvent for a Friedel-Crafts
reaction?
A) Chlorobenzene
B) Nitrobenzene
C) Acetophenone
D) (Trifluoromethyl)benzene
E)
All could be used.
Ans: A
Section: 15.8
17. Undesired polysubstitution of an aromatic nucleus is most likely to be encountered in
the case of:
A) Friedel-Crafts alkylation
B) Friedel-Crafts acylation
C) Nitration
D) Sulfonation
E)
Chlorination
Ans: A
51

Section: 15.8
18. This molecule does not normally participate as a reactant in a Friedel-Crafts reaction.
A) Benzene
B) Chlorobenzene
C) Nitrobenzene
D) Toluene
E)
tert-Butylbenzene
Ans: C
Section: 15.8
19. Which one of these molecules can be a reactant in a Friedel-Crafts reaction?
A) Aniline
B) Nitrobenzene
C) Chloroethene
D) Bromobenzene
E)
p-Bromonitrobenzene
Ans: D
Section: 14.2, 15.3, and 15.8
20. A mixture of chlorobenzene (1 mol) and acetanilide (1mol) is allowed to react with Br2
(0.5 mol) in the presence of trace amounts of FeBr3. What is the principal product of the
competing reactions?
A) 1-bromo-4-chlorobenzene
B) 1-bromo-2-chlorobenzene
C) 1-bromo-3-chlorobenzene
D) 4-bromoacetanilide
E)
3-bromoacetanilide
Ans: D
52
Topic: Reaction Products

21. Which of the following reactions would give the product(s) indicated in substantial
amounts (i.e., in greater than 50% yield)?
N H
NH
C H 3C l
A lC l3
and
CH
N H
II
C H 3C l
III
A)
B)
C)
D)
E)
Ans:
I
II
III
All of these
None of these
E
A lC l3
C H 3C H 2C H 2C l
53
C H
C H
A lC l3
N H
N H
C H 2C H 2C H

22. What would you expect to be the major product obtained from the following reaction?
O
excess
A)
B)
C)
D)
E)
Ans:
HN
AlCl3
CH3Cl
HN
HN
HN
II
III
HN
HN
IV
I
II
III
IV
V
E
54

23. The reaction of benzene with (CH3)3CCH2Cl in the presence of anhydrous aluminum
chloride produces principally which of these?
II
IV
A)
B)
C)
D)
E)
Ans:
III
I
II
III
IV
V
E
55

24.
Cl in the presence of anhydrous aluminum
The reaction of benzene with
II
IV
A)
B)
C)
D)
E)
Ans:
III
I
II
III
IV
V
D
56

25.
Cl
The reaction of benzene with

in the presence of anhydrous aluminum
II
III
IV
A)
B)
C)
D)
E)
Ans:
I
II
III
IV
V
A
57

O 2N
AlCl3
O2 N
O
II
O 2N
III
O 2N
IV
A)
B)
C)
D)
E)
Ans:
O2N
O2N
O
Cl
I
II
III
IV
V
A
58

27. The major product(s) of the following reaction,
O
O
AlCl3
Cl
O
O
O
O
II
III
IV
would be:
A) I
B) II
C) III
D) IV
E)
V
Ans: E
59

28. What might be predicted to happen when the following substance undergoes FriedelCrafts acylation?
O2N
CH2
A
B
A) Substitution occurs in ring B, p- to the methylene group.
B) Substitution occurs in ring A, o- to the nitro group.
C) Substitution occurs in ring A, o- to the methylene group.
D) Substitution occurs in ring B, m- to the methylene group.
E)
None of the above. No reaction will occur.
Ans: A
29. What would be the product of the following reaction sequence?
OH
i) SOCl2
?
ii) C6H6, AlCl3
O
iii) Zn(Hg), HCl, heat
O
OH
OH
II
IV
A)
B)
C)
D)
E)
Ans:
III
I
II
III
IV
V
E
60

OH
O
i) PCl5
ii) C6H6, AlCl3
OH
OH
II
IV
A)
B)
C)
D)
E)
Ans:
III
I
II
III
IV
V
E
61

OH
i) SOCl2
ii) C6H6, AlCl3
OH
II
III
O
OH
IV
A)
B)
C)
D)
E)
Ans:
I
II
III
IV
V
B
62

32. Which would be the product of the following reaction sequence?
O
i) SOCl2
?
OH ii) benzene, AlCl3
iii) Zn(Hg), HCl
SO2
CO2
CH2
II
III
IV
A)
B)
C)
D)
E)
Ans:
I
II
III
IV
V
C
63

33. Which would be the product of the following reaction sequence?
O
i) PCl5
?
ii) benzene, AlCl3
OH
iii) Zn(Hg), HCl
SO2
CO2
CH2
II
III
IV
A)
B)
C)
D)
E)
Ans:
I
II
III
IV
V
C
64

34. Which would be the product, X, of the following reaction sequence?
O
Ph
O
Ph
i) benzene, AlCl3
ii) Zn(Hg), HCl
OH
SO2
CO2
CH2
II
III
IV
A)
B)
C)
D)
E)
Ans:
I
II
III
IV
V
C
Topic: Directing Effects

Section: 15.10
35. Which of the following is not a meta-directing substituent when present on the benzene
ring?
A) -NHCOCH3
B) -NO2
C) -N(CH3)3+
D) -CN
E)
-CO2H
Ans: A
65

Section: 15.10
36. Which of the following compounds would yield the greatest amount of meta product
when subjected to ring nitration?
HO
O
HO
O
HO
I
A)
B)
C)
D)
E)
Ans:
I
II
III
IV
V
A
HO
OH
II
IV
III

Section: 15.10
37. Which of the following is not an ortho-para director in electrophilic aromatic
substitution?
A) -CF3
B) -OCH3
C) -CH3
D) -F
E)
-NH2
Ans: A
66

Section: 15.10
38. Which is the best prediction of the site(s) of substitution when 3-methylphenol is
nitrated?
A) C-2
B) C-4
C) C-5
D) C-6
E)
C-4 and C-6
Ans: E
Section: 15.10
39. (Trifluoromethyl)benzene, C6H5CF3, will
A) nitrate rapidly in the ortho-para positions.
B) nitrate slowly in the ortho-para positions.
C) nitrate rapidly in the meta position.
D) nitrate slowly in the meta position.
E)
fail to nitrate under any conditions.
Ans: D
Section: 15.10
40. Which of these compounds gives essentially a single product on electrophilic
substitution of a third group?
A) p-chlorotoluene
B) m-ethylanisole
C) 1-bromo-2-chlorobenzene
D) m-xylene
E)
3-hydroxybenzoic acid
Ans: D
67

Section: 15.10
41. Arrange the following compounds in order of decreasing reactivity in electrophilic
substitution:
O
I
A)
B)
C)
D)
E)
Ans:
II
V > II > I > III > IV
II > V > III > I > IV
IV > I > III > V > II
III > II > I > IV > V
IV > V > II > I > III
B
Br
NO2
IV
III
68

42. The major product(s), D, of the following reaction,
O
C
C H
B r2
2
F e B r3
O
Br
C H
C H
Br
II
O
C
O
C H
C H
Br
III
IV
would be:
A) I
B) II
C) III
D) IV
E)
Approximately equal amounts of I and II
Ans: D
69
Br

C O O H
B r2
S O 3H
C O O H
Br
S O 3H
I
A)
B)
C)
D)
E)
Ans:
F e B r3
C O O H
C O O H
C O O H
Br
Br
S O 3H
Br
S O 3H
II
III
I
II
III
IV
Equal amounts of II and IV
C
S O 3H
IV
70

N O
B r2
N O
N O
Br
S O 3H
I
A)
B)
C)
D)
E)
Ans:
Br
N O
S O 3H
F e B r3
S O 3H
Br
N O
Br
S O 3H
II
III
I
II
III
IV
C
S O 3H
IV
71

O
Br2, FeBr3
Br
O
Br
Br
II
III
Br
O
Br
IV
A)
B)
C)
D)
E)
Ans:
I
II
III
IV
V
D
72

1 equiv. Br2
FeBr3
Br
Br
II
Br
III
Br
Br
IV
A)
B)
C)
D)
E)
Ans:
I
II
III
IV
V
C
73

1 equiv. Cl2
FeCl3
Cl
Cl
Cl
II
III
Cl
Cl
IV
A)
B)
C)
D)
E)
Ans:
I
II
III
IV
V
C
74

O
Cl2, FeCl3
HN
?
Cl
HN
HN
II
III
Cl
HN
Cl
I
O
HN
HN
IV
A)
B)
C)
D)
E)
Ans:
Cl
I
II
III
IV
V
E
75
Cl

1 equivalent Br2
O
FeBr3
Br
O
Br
III
II
Br
O
O
Br
IV
A)
B)
C)
D)
E)
Ans:
I
II
III
IV
V
C
76
Br

50. What would you expect to be the major product obtained from the monobromination of
m-dichlorobenzene?
Cl
Cl
Cl
Br
Cl
Cl
Br
Br
II
A)
B)
C)
D)
E)
Ans:
Cl
III
I
II
III
Equal amounts of I and II
Equal amounts of I, II and III
B

51. Which would be the major product(s) of the following reaction?
H3CO
Br2, FeBr3
H3CO
H3CO
H3CO
Br
Br
A)
B)
C)
D)
E)
Ans:
Br2Fe
II
III
I
II
III
I and II in roughly equal amounts
I and III in roughly equal amounts
A
77
Topic: Reagents
52. Which reagent(s) would you use to carry out the following transformation?
isopropylbenzene
2- and 4-chloro-1-isopropylbenzene
A) Cl2, light, and heat
B) Cl2, FeCl3
C) SOCl2
D) C2H5Cl, AlCl3
E)
HCl, peroxides
Ans: B
Topic: Reagents
ethylbenzene
2- and 4-chloro-1-ethylbenzene
B) Cl2, FeCl3
C) SOCl2
D) C2H5Cl, AlCl3
E)
None of these
Ans: B
Topic: Reagents
t-butylbenzene
p-chloro substitution product
B) Cl2, FeCl3
C) SOCl2
D) C2H5Cl, AlCl3
E)
HCl, peroxide
Ans: B
78
Topic: Reagents
55. Which reagent(s) would you use to synthesize 2- and 4-bromo-1-cyclopentylbenzene
from cyclopentylbenzene?
A) N-Bromosuccinimide (NBS), CCl4, light
B) PBr3
C) Br2, FeBr3
D) CH3CH2Br, AlBr3
E)
HBr, ROOR
Ans: C
Topic: Reagents
cumene
2- and 4-chlorocumene
B) Cl2, FeCl3
C) SOCl2
D) C2H5Cl, AlCl3
E)
HCl, peroxides
Ans: B
79

O
HNO3
H2SO4, heat
HN
O2N
HN
O2N
A)
B)
C)
D)
E)
Ans:
NO2
O
HN
HN
II
III
HN
HN
IV
NO2
I
II
III
IV
V
E
80
NO2

O
HNO3
H2SO4, heat
O2N
O
O2N
II
III
NO2
O
O
O
IV
A)
B)
C)
D)
E)
Ans:
NO2
I
II
III
IV
V
C
81
NO2

59. What would be the major product(s) of the following reaction?
CO2H
HNO3
NO2 H2SO4, heat
CO2H
NO2
NO2
I
A)
B)
C)
D)
E)
Ans:
CO2H
NO2
NO2
II
CO2H
O2N
O2N
CO2H
NO2
NO2
IV
III
I
II
III
IV
Approximately equal amounts of II and IV
C
82

1 equiv. HNO3
H2SO4, heat
O2N
NO2
II
NO2
III
NO2
O2N
IV
A)
B)
C)
D)
E)
Ans:
I
II
III
IV
V
C
83

HNO3
H2SO4, heat
HN
O2 N
HN
HN
HN
O2N
II
III
NO2
HN
HN
IV
A)
B)
C)
D)
E)
Ans:
NO2
I
II
III
IV
V
A
84
NO2

62. What would you expect to be the major product(s) obtained from the mononitration of
m-dichlorobenzene?
Cl
Cl
Cl
I
A)
B)
C)
D)
E)
Ans:
Cl
NO2
Cl
NO2
O2N
Cl
II
III
I
II
III
Equal amounts of I, II and III
B

63. What would you expect to be the major product(s) obtained from the following
reaction?
HO
HNO3
H2SO4 , heat
SO3H
HO
HO
HO
HO
NO2
SO3H
I
A)
B)
C)
D)
E)
Ans:
O2N
SO3H
O2N
NO2
II
SO3H
SO3H
IV
III
I
II
III
IV
C
85

64. The major product(s), D, of the following reaction
O
H N O
H 2S O
O
O 2N
N O
II
N O
O
N O
III
IV
would be:
A) I
B) II
C) III
D) IV
E)
Ans: D
86

HO
HNO3
H2SO4
HO
HO
HO
NO2
NO2
I
A)
B)
C)
D)
E)
Ans:
HO3S
II
III
I
II
III
A
87

H3CO
HNO3
H2SO4
H3CO
H3CO
H3CO
NO2
NO2
A)
B)
C)
D)
E)
Ans:
HO3S
III
II
I
II
III
A
88

O
HNO3
H2SO4, heat
N
N
O2N
N
N
NO2
O
N
O 2N
II
III
O
O
N
N
IV
A)
B)
C)
D)
E)
Ans:
NO2
I
II
III
IV
V
E
89
NO2

O
H2SO4
NO2
O
SO3H
NO2
I
A)
B)
C)
D)
E)
Ans:
HO3S
NO2
SO3H
HO3S
II
NO2
NO2
IV
III
I
II
III
Equal amounts of I and IV
C
90

O
H2SO4
SO3
NO2
O
HO3S
SO3H
NO2
A)
B)
C)
D)
E)
Ans:
NO2
SO3H
HO3S
II
NO2
NO2
III
I
II
III
Equal amounts of I and IV
C
91
IV

70. The major product(s), C, of the following reaction,
C l
SO 3
H 2S O
C l
C l
C l
C l
S O 3H
Cl
C l
S O 3H
II
H O 3S
C l
III
would be:
A) I
B) II
C) III
D) Approximately equal amounts of I and II
E)
Approximately equal amounts of I and III
Ans: B
Topic: Reagents
71. Which reagent would you use to carry out the following transformation?
tert-butylbenzene
p-tert-butylbenzenesulfonic acid
+
o-tert-butylbenzenesulfonic acid
A) HNO3/H2SO4
B) tert-C4H9Cl/AlCl3
C) H2SO3/peroxides
D) SO3/H2SO4
E)
SO2/H2SO3
Ans: D
92
Topic: Relative Reactivities

Section: 15.11
72. Which of the following compounds would be most reactive toward electrophilic
substitution?
OH
CH3
II
A)
B)
C)
D)
E)
Ans:
Br
III
CHO
NO2
IV
I
II
III
IV
V
A

Section: 15.11
73. Which of the following compounds would be least reactive toward electrophilic
substitution?
OH
CH3
II
A)
B)
C)
D)
E)
Ans:
Br
III
I
II
III
IV
V
E
93
CHO
NO2
IV

Section: 15.11
74. Which of the following compounds would be most reactive to ring bromination?
NO2
CH3
I
A)
B)
C)
D)
E)
Ans:
CF3
II
Cl
NH2
IV
III
I
II
III
IV
V
E

Section: 15.11
75. Which of the following compounds would be least reactive toward electrophilic
substitution?
O
O
NO2
NO2
I
A)
B)
C)
D)
E)
Ans:
NH
I
II
III
IV
V
B
II
IV
III
94

Section: 15.11
76. Which of the following compounds would be most reactive toward electrophilic
substitution?
O
O
NO2
NH2
NH
NO2
A)
B)
C)
D)
E)
Ans:
IV
III
II
I
II
III
IV
V
E

Section: 15.11
77. Which of the following compounds would be most reactive toward ring nitration?
O
O
O
I
A)
B)
C)
D)
E)
Ans:
II
I
II
III
IV
V
D
CF3
III
95
OH
NH
IV

Section: 15.11
78. Which of the compounds listed below would you expect to give the greatest amount of
meta-product when subjected to ring bromination?
HO
OH
NH2
II
I
A)
B)
C)
D)
E)
Ans:
III
OCH3
CH3
IV
I
II
III
IV
V
B

Section: 15.11
79. Which of the following compounds would be most reactive toward ring bromination?
O
HO
NH2
OCH3
II
I
A)
B)
C)
D)
E)
Ans:
IV
III
I
II
III
IV
V
C
96

Section: 15.11
80. Which of the compounds listed below would you expect to give the greatest amount of
meta-product when subjected to ring nitration?
O
I
A)
B)
C)
D)
E)
Ans:
II
NH
III
I
II
III
IV
V
B
97
OCH3
CH3
IV

Section: 15.11
81. Which of the following structures contribute(s) to the resonance hybrid of the
intermediate formed when bromobenzene undergoes para-chlorination?
..
..
..
..
: Br :
: Br +
: Br :
: Br :
+
+
+
H Cl
H Cl
H Cl
H Cl
II
III
IV
A)
B)
C)
D)
E)
Ans:
I
II
III
IV
All of the above
E
98

Section: 15.11
intermediate formed when chlorobenzene undergoes para-chlorination?
..
..
..
..
: Cl :
: Cl +
: Cl :
: Cl :
+
+
+
H Cl
H Cl
H Cl
H Cl
II
III
IV
A)
B)
C)
D)
E)
Ans:
I
II
III
IV
All of the above
E

Section: 15.11
intermediate formed when acetanilide undergoes para-bromination?
+NCOCH
:NHCOCH3
: NHCOCH3
: NHCOCH3
3
+
+
+
H Br
H Br
H Br
H Br
II
III
IV
A)
B)
C)
D)
E)
Ans:
I
II
III
IV
All of the above
E
99

Section: 15.11
84. Which of the following contributors to the resonance stabilized hybrid formed when
aniline undergoes para-chlorination would be exceptionally stable?
+NH2
: NH2
: NH2
: NH2
+
+
+
H Cl
H Cl
H Cl
H Cl
II
III
IV
A)
B)
C)
D)
E)
Ans:
I
II
III
IV
None of these
B

Section: 15.11
85. Consider the structures given below. Which of them would be a relatively stable
contributor to the hybrid formed when toluene undergoes para bromination?
A)
B)
C)
D)
E)
Ans:
I
II
III
IV
V
C
100

Section: 15.11
86. Which of the following structures does not contribute to the resonance hybrid of the
intermediate formed when nitrobenzene undergoes meta-chlorination?
..
..
..
..
..
..
:O : O:
: O : O:
: O : O:
N
+
I
A)
B)
C)
D)
E)
Ans:
H
Cl
+H
H
Cl
II
Cl
III
I
II
III
None of these contribute
All of these contribute
E

Section: 15.11
87. Which of the following compounds would you expect to be most reactive toward ring
nitration?
A) Benzene
B) Toluene
C) m-Xylene
D) p-Xylene
E)
Benzoic acid
Ans: C
101

Section: 15.11
88. Which of the following compounds would you expect to be most reactive toward ring
nitration?
A) Benzene
B) Toluene
C) m-Xylene
D) o-Xylene
E)
Benzoic acid
Ans: C
Section: 15.11
89. What is a feature found in all ortho-para directing groups?
A) An oxygen atom is directly attached to the aromatic ring.
B) The atom attached to the aromatic ring possesses an unshared pair of electrons.
C) The group has the ability to delocalize the positive charge of the arenium ion.
D) The atom directly attached to the aromatic ring is more electronegative than
carbon.
E)
The group contains a multiple bond.
Ans: C
90. What feature is common to all meta-directing groups?
A) The atom directly attached to the ring has a full or well-developed partial positive
charge.
B) The atom directly attached to the ring is doubly bonded to oxygen.
C) One or more halogen atoms are present in the group.
D) One or more oxygen atoms are present in the group.
E)
The group is attached to the ring through a carbon atom.
Ans: A
102

91. This substituent deactivates the benzene ring towards electrophilic substitution but
directs the incoming group chiefly to the ortho and para positions.
A) -OCH2CH3
B) -NO2
C) -F
D) -CF3
E)
-NHCOCH3
Ans: C
Section: 15.12
92. The major product(s), A, of the following reaction,
C H 3C H
C H 3C H
C l2 , h
2
C l
4 0 0 - 6 0 0 oC
C H 3C H
C lC H 2 C H
C l
C l
C H 3C H
II
III
would be:
A) I
B) II
C) A mixture of I and II
D) III
E)
IV
Ans: E
103
IV

Section: 15.12
excess Cl2
400o - 600oC
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
II
A)
B)
C)
D)
E)
Ans:
IV
III
I
II
A mixture of I and II
III
IV
A
104

Section: 15.12
excess NBS
?
ROOR
Br
Br
Br
Br
Br
Br
Br
Br
A)
B)
C)
D)
E)
Ans:
II
III
I
II
A mixture of I and II
III
IV
D
105
IV

Section: 15.12
95. The major product(s), A, of the following reaction,
NBS
?
ROOR
Br
Br
Br
Br
II
IV
III
would be:
A) I
B) II
C) A mixture of I and II
D) III
E)
IV
Ans: E
Section: 15.12
96. What would be the major product of the following reaction?
C H 2C H 2C H
C l
C H 2C H 2C H
C l
C H 2C H C H
IV
C l
400 oC
C H 2C H 2C H
A)
C l2
C H C H 2C H
Cl
II
III
C H 2C H 2C H 2C l
106
B)
C)
D)
E)
Ans:
II
III
IV
V
C

Section: 15.12
107
NBS
?
ROOR
Br
Br
Br
A)
B)
C)
D)
E)
Ans:
II
Br
Br
III
I
II
III
IV
V
D
108
IV

Section: 15.12
excess NBS
?
ROOR
Br
Br
Br
Br
Br
Br
Br
Br
III
II
Br
Br
IV
A)
B)
C)
D)
E)
Ans:
I
II
III
IV
V
C
109
IV

Section: 15.12
Cl2
peroxides
Cl
Cl
Cl
II
III
Cl
Cl
IV
A)
B)
C)
D)
E)
Ans:
I
II
III
IV
V
E
110

Section: 15.12
Cl2
light
Cl
Cl
Cl
II
III
Cl
Cl
IV
A)
B)
C)
D)
E)
Ans:
I
II
III
IV
V
E
111

Section: 15.12
101. 4 of the following reaction?
NBS, ROOR
light
Br
Br
Br
II
III
Br
Br
IV
A)
B)
C)
D)
E)
Ans:
I
II
III
IV
V
C
Topic: Reagents
Section: 15.12
ethylbenzene
1-chloro-1-phenylethane
A) Cl2, light, or heat
B) Cl2, FeCl3
C) SOCl2
D) C2H5Cl, AlCl3
E)
HCl, O2
Ans: A
112
Topic: Non-EAS Relative Rates and Intermediates

Section: 15.12
103. Which of the following structures would not be a contributor to the resonance hybrid of
the benzyl cation?
CH3
H
H
+
I
A)
B)
C)
D)
E)
Ans:
+CH2
CH3
CH2
+
IV
III
I
II
III
IV
V
A

Section: 15.12
104. Which of the following carbocations would be most stable?
CH 3
A)
C 6H 5C H 2C H 2C H C H
C)
C H
C 6H 5C H 2C H 2C C H
C H
E)
C 6H 5C H 2C H 2C H C H
CH 3
D)
+
II
B)
CH3
C 6H 5C H 2C H C H C H
C H 3
C 6H 5C H C H 2C H C H
Ans: E
113
IV
Topic: Reagents
Section: 15.12
toluene
benzyl bromide
A) Br2, FeBr3
B) N-Bromosuccinimide, ROOR, h
C) HBr
D) Br2/CCl4
E)
NaBr, H2SO4
Ans: B
106. When toluene is reacted in turn with 1) Cl2 (large excess), heat, and light and 2)
Br2,FeBr3, the chief product is:
Br
CCl3
A)
B)
C)
D)
E)
Ans:
CCl3
Br
Cl
CCl3
Br
Br
II
III
IV
I
II
III
IV
A mixture of III and IV
B
114
Topic: Synthesis
Section: 15.13
107. Benzoic acid can be prepared by the oxidation of all of the following compounds except
this one:
A) C6H5CH=CH2
B) C6H5CCH
C) C6H5COCH3
D) C6H5CH2CH2CH3
E)
C6H5C(CH3)3
Ans: E
Topic: Synthesis
Section: 15.13
108. Benzoic acid can be prepared by the oxidation of which of the following compounds:
A) C6H5CH=CH2
B) C6H5CCH
C) C6H5COCH3
D) C6H5CH2CH2CH3
E)
All of these
Ans: E
Topic: Reagents
Section: 15.13
toluene
benzoic acid
A) Br2, heat, and light
B) Cl2, FeCl3
C) KMnO4, OH-, heat (then H3O+)
D) HNO3/H2SO4
E)
SO3/H2SO4
Ans: C
115
Topic: Reagents
Section: 15.13
ethylbenzene
benzoic acid
B) Cl2, FeCl3
C) KMnO4, OH-, heat (then H3O+)
D) HNO3/H2SO4
E)
SO3/H2SO4
Ans: C
Topic: Synthesis
Section: 15.13
111. Which of these is a satisfactory synthesis of 1-bromo-2-phenylethane?
A) C6H5CH2CH3 + Br2, Fe3+
B) C6H5CH2CH3 + Br2, 400C
C) C6H5CH2CH2OH + Br2, CCl4
D) C6H5CH=CH2 + HBr, ROOR
E)
C6H5CH2CH3 + NBS, ROOR
Ans: D
116

Section: 15.3, 15.4, 15.10, and 15.13
112. Toluene is subjected to the action of the following reagents in the order given: (1)
KMnO4,OH-, heat; then H3O+ (2) HNO3, H2SO4 (3) Br2, FeBr3
What is the final product of this sequence?
CO2H
Br
CO2H
NO2
Br
NO2
Br
II
III
Br
Br
A)
B)
C)
D)
E)
Ans:
CO2H
NO2
CH3
NO2
NO2
CO2H
IV
I
II
III
IV
V
A
117

Section: 15.3, 15.4, 15.10, and 15.13
113. Toluene is subjected to the action of the following reagents in the order given: (1)
KMnO4,OH-, heat; then H3O+ (2) HNO3, H2SO4 (3) Cl2, FeCl3
What is the final product of this sequence?
CO2H
Br
CO2H
NO2
Br
NO2
Br
II
III
Br
Br
A)
B)
C)
D)
E)
Ans:
CO2H
NO2
CH3
NO2
NO2
CO2H
IV
I
II
III
IV
V
D
118
Topic: Reaction products

Section: 15.6, 15.12, 15.13 and previous chapters
114. What product would result from the following series of reactions,
i) AlCl3
ii) N-Bromosuccinimide, peroxides
iii) CH3ONa, CH3OH, heat
iv) m-CPBA
v) CH3MgBr
vi) NH4Cl
Cl
Br
HO
HO
II
I
HO
IV
A)
B)
C)
D)
E)
Ans:
III
HO
I
II
III
IV
V
D
119

i) HF
iv) m-CPBA
v) CH3MgBr
vi) NH4Cl
Br
HO
HO
II
I
HO
IV
A)
B)
C)
D)
E)
Ans:
III
HO
I
II
III
IV
V
D
120

i) BF3
iv) m-CPBA
v) CH3MgBr
vi) NH4Cl
OH
Br
HO
HO
II
I
HO
IV
A)
B)
C)
D)
E)
Ans:
III
HO
I
II
III
IV
V
D
121
Topic: Synthesis
Section: 15.13C
117. What reagent can effect the following transformation?
Br
CO2H
Br
CO2H
Br
A)
B)
C)
D)
E)
Ans:
CO2; then H3O+

H3O+, heat
Mg; then CO2; then H3O+
H2O2, heat
KMnO4, OH-, heat; then H3O+
E
Br
CO2H

Section: 15.14
118. Each of the five disubstituted benzenes shown below is nitrated. In which of these cases
does the arrow not indicate the chief position of nitration.
C l
C O O H
C l
N H C O CH
C l
N O
O H
A)
B)
C)
D)
E)
Ans:
I
I
II
III
IV
V
C
II
C H
III
IV
122
O
3
C C H
C H 2C H
Topic: Synthesis
Section: 15.14
119. A good synthesis of
O
(C H 3)3C
would be:
A)
B enzene
CCH
O
C H 3C C l
(C H 3)3C C l
A lC l3
A lC l3
O
B)
B enzene
(C H 3)3C C l
C H 3C C l
A lC l3
A lC l3
C)
B enzene
C H 3C C l
A lC l3
D) More than one of these
E)
None of these
Ans: B
(C H 3)2C
H F
123
C H
Topic: Synthesis
Section: 15.14
120. Which would be a good synthesis of m-nitrobenzoic acid?
A)
H N O 3 /H 2 S O 4
C H 3C l
1. K M nO 4, N aO H , h eat
B enzene
heat
A lC l3
2. H 3O +
B)
C)
H N O 3/H 2S O
T o lu e n e
1 . K M n O 4, N aO H , h eat
heat
2 . H 3O
1 . K M n O 4, N aO H , h e at
T o lu e n e
2 . H 3O +
D) More than one of the above
E)
None of the above
Ans: C
H N O 3 /H 2 S O
heat
Topic: Reagents
Section: 15.14
121. The compound 4-bromo-1-propylbenzene is best made from benzene by the application
of these reagents in the order shown:
A) (1) Br2,Fe (2) CH3CH2CH2Cl, AlCl3
B) (1) CH3CH2CH2Cl, AlCl3 (2) Br2,Fe
C)
1 ) C H 3C H 2C C l, A lC l3 2 ) B r2 , F e 3 ) Z n (H g ), H C l
D)
1 ) C H 3C H 2C C l, A lC l3
2 ) Z n (H g ), H C l
E)
(1) (CH3)2CHCl, AlCl3 (2) Br2,Fe
Ans: D
124
3 ) B r2, F e
Topic: Nomenclature, Synthesis

Section: 15.14
122. Which of the following would be the best synthesis of 1,4-dimethyl-2-nitrobenzene?
A)
H N O 3
2 C H 3C l
B enzene
p ro d u ct
2 A lC l3
H 2S O 4
H N O 3
C H 3C l
B)
T o lu e n e
p ro d u ct
A lC l3
H 2S O 4
H N O 3
C)
p -X y le n e
H 2S O 4
C H 3C l
D)
m - N itro to lu e n e
A lC l3
E)
All of these are equally good.
Ans: C
Topic: Synthesis
Section: 15.14
123. Starting with benzene, the best method for preparing p-nitrobenzoic acid is:
A) HNO3/H2SO4; then CH3Cl/AlCl3; then separation of isomers; then KMnO4/
OH/heat, followed by H3O+.
B) CH3Cl/AlCl3; then HNO3/H2SO4; then separation of isomers; then KMnO4/
C) CH3Cl/AlCl3; then KMnO4/-OH/heat, followed by H3O+; then HNO3/H2SO4.
D) HNO3/H2SO4; then KMnO4/-OH/heat, followed by H3O+; then CH3Cl/AlCl3.
E)
HNO3/H2SO4; then CO2, followed by H3O+.
Ans: B
125
Topic: Synthesis
Section: 15.14
124. Starting with benzene, the best method for preparing m-nitrobenzoic acid is:
A) HNO3/H2SO4; then CH3Cl/AlCl3; then separation of isomers; then KMnO4/
B) CH3Cl/AlCl3; then HNO3/H2SO4; then separation of isomers; then KMnO4/
C) CH3Cl/AlCl3; then KMnO4/-OH/heat, followed by H3O+; then HNO3/H2SO4.
D) HNO3/H2SO4; then KMnO4/-OH/heat, followed by H3O+; then CH3Cl/AlCl3.
E)
HNO3/H2SO4; then CO2, followed by H3O+.
Ans: C
126
Topic: Synthesis
Section: 15.14
125. How might the following synthesis be carried out:
se v eral
s te p s
C H 3C H 2C l
B enzene
A)
B)
C 6H
C 6H
A lC l3
C l2
F e C l3
O
C)
C 6H
C 6H
?
C l
C l2
F e C l3
C H 3C H 2C l
A lC l3
p ro d u ct
p ro d u ct
C H 3C C l
C l2
Z n (H g )
A lC l3
F e C l3
H C l
C H 3C C l
Z n (H g )
C l2
D)
C H 2C H
A lC l3
H Cl
E)
None of these syntheses is satisfactory.
Ans: C
127
F e C l3
p ro d u ct
p ro d u ct
Topic: Synthesis
Section: 15.14
126. How might the following synthesis be carried out:
several
steps
A)
B)
Cl
C H 3C H 2C l
C 6H
C 6H
A lC l3
C l2
F e C l3
O
C)
C 6H
C 6H
F e C l3
C H 3C H 2C l
A lC l3
p ro d u ct
p ro d u ct
C H 3C C l
C l2
Z n (H g )
A lC l3
F e C l3
H C l
C H 3C C l
Z n (H g )
C l2
D)
C l2
A lC l3
H Cl
E)
Ans: D
128
F e C l3
p ro d u ct
p ro d u ct
Topic: Synthesis
Section: 15.14
127. Which is the best sequence of reactions for the preparation of p-bromostyrene from
ethylbenzene?
A)
N B S, h
B r2
K O H
p ro d u c t
e th y lb e n z e n e
C C l4
Fe
C H 3C H 2O H
B)
B r2
N B S, h
K O H
p ro d u c t
Fe
C C l4
C H 3C H 2O H
C)
N B S, h
K O H
B r2
p ro d u c t
C C l4
C H 3C H 2O H
Fe
ZnO
B r2
D)
p ro d u c t
63 0 oC
Fe
E)
Ans: B
Topic: Synthesis
Section: 15.14 and previous chapters
128. Which is the best sequence of reactions for the following transformation?
O
NO2
A)
B)
C)
D)
E)
Ans:
i) HNO3, H2SO4; ii) CH3MgBr, Et2O; iii) H3O+, heat

i) CH3MgBr, Et2O; ii) H3O+, heat; iii) HNO3, H2SO4
i) HNO3, H2SO4; ii) NaBH4, H2O; iii) H3O+, heat
i) HNO3, H2SO4; ii) LiAlH4, H2O; iii) H3O+, heat
A
129
Topic: Synthesis
O
OH
NO2
A)
B)
C)
D)
E)
Ans:
i) HNO3, H2SO4; ii) CH3MgBr, Et2O; iii) H2O, NH4Cl

A
Topic: Synthesis
O
OH
NO2
A)
B)
C)
D)
E)
Ans:
i) HNO3, H2SO4; ii) CH3MgBr, Et2O; iii) H2O, NH4Cl

A
130
Topic: Synthesis
O
NO2
A)
B)
C)
D)
E)
Ans:
i) HNO3, H2SO4; ii) CH3MgBr, Et2O; iii) H3O+, heat

i)HNO3, H2SO4; ii) LiAlH4, H2O; iii) H3O+, heat
A
Topic: Synthesis
OH
O
OCH3
NO2
A)
B)
C)
D)
E)
Ans:
i) HNO3, H2SO4; ii) 2EtMgBr, Et2O; iii) NH4Cl

i) 2EtMgBr, Et2O; ii) H3O+; iii) HNO3, H2SO4
i) HNO3, H2SO4; ii) NaBH4, H2O; iii) 2EtMgBr, Et2O
i) LAH; ii) 2EtLi, Et2O; iii) HNO3, H2SO4, heat
A
131
Topic: Synthesis
O
OCH3
NO2
A)
B)
C)
D)
E)
Ans:
NO2
i) HNO3, H2SO4; ii) 2EtMgBr, Et2O; iii) NH4Cl

i) 2EtMgBr, Et2O; ii) H3O+; iii) HNO3, H2SO4
i) HNO3, H2SO4; ii) NaBH4, H2O; iii) 2EtMgBr, Et2O
i) LAH; ii) 2EtLi, Et2O; iii) HNO3, H2SO4, heat
A
Topic: Synthesis
Section: 15.14
O
OH
NO2
A)
B)
C)
D)
E)
Ans:
i) SOCl2; ii) C6H6, AlCl3; iii) Zn(Hg),HCl; iv) HNO3, H2SO4

i) SOCl2; ii) HNO3, H2SO4; iii) C6H6, AlCl3; iv) H2, Ni
i) HNO3, H2SO4; ii) SOCl2; iii) C6H6, AlCl3; iv) Zn(Hg),HCl
i) PBr3; ii) HNO3, H2SO4; iii) C6H6, AlCl3; iv) NaBH4, H2O
Two of these syntheses are satisfactory.
C
132

Section: 15.15
135. Which alkyl halide would be most reactive in an SN2 reaction?
A) C6H5CH2CH2CH2Br
C 6H 5C H C H 2B r
B)
C)
C H3
C 6H 5C H 2C H C H
C H
D)
Br
3
C 6H 5C C H 2B r
C H
Br
E)
C 6H 5C C H
C H
Ans: A
Section: 15.15
136. Which alkyl halide would be most reactive in an SN1 reaction?
A) C6H5CH2CH2CH2Br
C 6H 5C H 2C H C H 3
B)
Br
C H
C)
C 6H 5C H 2C B r
C H
Br
D)
C 6H 5C C H
C H
C H
E)
3
3
C 6H 5C C H 2B r
C H
Ans: D
133
Topic: Non-EAS Reactions

Section: 15.15
137. SN1 solvolysis of C6H5CH=CHCH2Cl in water produces:
A) C6H5CH2C(OH)=CH2
B) C6H5CH=CHCH2OH
C) C6H5CHOHCH=CH2
D) A mixture of B) and C)
E)
A mixture of A), B) and C)
Ans: D
Section: 15.15
138. Which compound is capable of undergoing both SN1 and SN2 reactions in ordinary
nonacidic solvents?
Br
Br
Br
Br
Br
A)
B)
C)
D)
E)
Ans:
I
I
II
III
IV
V
D
II
III
134
IV

Section: 15.15
139. Which alkyl halide can undergo both SN1 and SN2 reactions in nonacidic solvents?
A) CH3Br
B) CH3CH2CH2Br
CH 2
CHC HC H 3
C)
D)
E)
Br
C6H5CH2CH2CH2Br
C H
C 6H 5C C H 2B r
C H
Ans: C
Section: 15.15
140. The rate of solvolysis in ethanol is least for which of these compounds?
A) C6H5CH2Cl
C 6 H 5C (C H 3)2
B)
C)
D)
C l
(C6H5)2CHCl
C 6H 5C H C l
C H
E)
(C6H5)3CCl
Ans: A
135

141. The ortho/para product ratio is expected to be the smallest for the bromination of which
of these?
A) Toluene
B) Isopropylbenzene
C) Butylbenzene
D) sec-Butylbenzene
E)
tert-Butylbenzene
Ans: E
Section: 15.16
142. What is the Birch reduction product of the following reaction?
Na, NH3(l)
EtOH
II
A)
B)
C)
D)
E)
Ans:
IV
III
I
II
III
IV
V
D
136

Section: 15.16
143. Which of these species is/are proposed as intermediate(s) in the mechanism for the
Birch reduction?
A) Radical
B) Carbanion
C) Radical anion
D) Both A) and B)
E)
All of A), B) and C)
Ans: E
SHORT ANSWER QUESTIONS
Topic: General Reactivity
144. Although benzene is susceptible to electrophilic attack, its special stability causes it to
undergo ______________ rather than ____________ reactions.
Ans: substitution; addition
Section: 15.2
145. Benzene is susceptible to electrophilic attack primarily because of its _____________.
Ans: exposed system
Topic: EAS Mechanism
Section: 15.2
146. In general, there are three steps to an electrophilic aromatic substitution reaction. These
are:
a) formation of an _____________;
b) reaction with an aromatic ring to form an ___________; and
c) loss of a _________ to reform the aromatic system.
Ans: electrophile; arenium ion; proton
137
Topic: Synthetic Strategy

147. Suggest a reasonable synthetic strategy for the synthesis of 4-methyl-1-phenyl-1pentanol from 4-methylpentanoyl chloride, (CH3)2CHCH2CH2COCl
O
OH
Ans:
NaBH4
Cl
H2O
AlCl3
O
4-methylpentanoyl chloride
4-methyl-1-phenyl-1-pentanol

Section: 15.8
148. Aryl and vinyl halides cannot be used in the Friedel-Crafts alkylation because they do
not __________.
Ans: form carbocations readily
Topic: Mechanism, Carbocation Stability
149. Draw a mechanism that explains the formation of the following product in this FriedelCrafts alkylation:
AlCl3
+
Cl
Ans:
+
AlCl3
C
H2
Cl
Cl
AlCl3
-H+
Topic: General EAS Reactivity
138
AlCl4-
Section: 15.10
150. Substituent groups affect both _____________ and _______________ in electrophilic
aromatic substitution reactions.
Ans: reactivity; orientation
Section: 15.10
151. Electron-donating groups increase the electron density on the aromatic ring, causing it
to be more reactive than benzene itself towards EAS. These types of groups are called
_____________ groups.
Ans: activating
Section: 15.10
152. Electron-withdrawing groups decrease the electron density on the aromatic ring, causing
it to be less reactive than benzene itself towards EAS. These types of groups are called
_____________ groups.
Ans: deactivating
Section: 15.10
153. With the exception of halogens, activating groups are ____________ directors and
deactivating groups are _________ directors.
Ans: ortho/para; meta
139

154. Based on your knowledge of electrophilic aromatic substitution, predict the preferential
position of attack of an electrophile on furan, i.e., does the electrophile E+ attack carbon
2, or 3? Explain your answer.
E
E+
2
or
(-H )
Which substitution product forms preferentially and why?

Ans:
The 2 substitution product is favored since it comes from the arenium ion intermediate
that is lower in energy/more stable (possesses three resonance forms vs. only two for the
3 substituted product), and hence will form faster.
E+
E
O
-H+
E
O
H
E
E+
O
E
E
-H+
O
140

155.
Based on your knowledge of electrophilic aromatic substitution, predict the preferential

position of attack of an electrophile on pyrrole, i.e., does the electrophile E+ attack carbon
2, or 3? Explain your answer.
E
E+
2
or
(-H+)
N
H
N
H
N
H

Ans:
E+
E
N
H
N
H
E
N
H
E
N
H
-H+
E
N
H
H
E
E+
N
H
E
E
N
H
N
H
141
-H+
N
H

156.

position of attack of an electrophile on thiophene, i.e., does the electrophile E+ attack
carbon 2, or 3? Explain your answer.
E
E+
2
or
(-H+)

Ans:
E+
E
S
-H+
E
S
H
E
E+
S
E
E
142
-H+
S

157.
Based on your knowledge of electrophilic aromatic substitution, predict the position of

attack of an electrophile on pyridine, i.e., does the electrophile E+ attack carbon 2, 3, or
4? Explain your answer.
E
N
1
E+
(-H+)
E
or
N
or
Which substitution product(s) forms and why?

Ans:
that is lower in energy/more stable (possesses three good resonance forms), and hence
will form faster.
H
H
N
E+
H
N
divalent, positively charged nitrogen

poor resonance structure
E+
E+
divalent, positively charged nitrogen

poor resonance structure
143

158.

position of nitration of naphthalene, i.e., does the NO2+ attack carbon 1, or 2? Explain
your answer.
NO2
1
2
NO2
NO2+
or
(-H+)

Ans:
that is lower in energy/more stable (possesses two benzylic type resonance forms vs. only
one for the 2 substituted product), and hence will form faster.
H
NO2
NO2
NO2+
the existance of this "homobenzylic"resonance form

contributes to the stability of this intermediate
NO2
(-H+)
H
NO2
NO2+
NO2
only one benzylic resonance

form can be drawn
144
(-H+)
Topic: General EAS Reactivity, Mechanisms, Energy Diagrams

159.
Using a potential energy diagram, explain/illustrate the preferential formation of the 3

substituted product instead of the 2 or 4 product in the electrophilic aromatic substitution
of pyridine.
E
N
1
E+
(-H+)
E
instead of
N
or
N
Ans:
that is lower in energy/more stable (possesses three good resonance forms), and hence
will form faster.
145

160.

nitrated product instead of the 2 nitrated product in the electrophilic aromatic nitration of
naphthalene.
NO2
1
2
NO2
NO2+
instead of
(-H+)
Ans:
that is lower in energy/more stable (possesses two benzylic type resonance forms vs. only
one for the 2 substituted product), and hence will form faster.
146

161.

substituted product instead of the 3 product in the electrophilic aromatic substitution of
furan.
E
E+
2
(-H+)
instead of
E
Ans:
3 substituted product), and hence will form faster
147

162.

pyrrole.
E
E+
2
N
H
instead of
(-H )
N
H
E
N
H
Ans:
148

163.

thiophene.
E
E+
2
(-H+)
instead of
S
E
S
Ans:
149

164.
Based on your knowledge of electrophilic aromatic substitution, and assuming the pyrrole
ring of indole (shown) is activated toward electrophilic aromatic substituted more so than
the benzenoid ring, predict the preferential position of attack of an electrophile, i.e., does
the electrophile E+ attack carbon 2, or 3? Explain your answer.
E
3
E+
(-H+)
N
H
or
E
N
H
N
H
indole

Ans:
3-substitution is preferred, since this leads to a carbocation intermediate that can be
resonance stabilized through the nitrogen, without loss of the benzenoid ring aromaticity.
This resonance form is lower in energy than those forming from the 2-substituted
product, which although can be resonance stabilized through the benzenoid aromatic ring,
produces resonance forms without aromaticity.
H
E+
N
H
N
H
E
N
H
E
N
H
-H+
N
H
-H
N
H
N
H
N
H
N
H
E+
N
H
150
N
H

165.
Based on your knowledge of electrophilic aromatic substitution, and assuming the furan
ring of benzo[b]furan (shown) is activated toward electrophilic aromatic substituted more
so than the benzenoid ring, predict the preferential position of attack of an electrophile,
i.e., does the electrophile E+ attack carbon 2, or 3? Explain your answer.
E
3
E+
(-H )
or
1
benzo[b]furan

Ans:
resonance stabilized through the oxygen, without loss of the benzenoid ring aromaticity.
H
E
E
E+
O
-H
E+
E
O
-H+
O
151

166.
Based on your knowledge of electrophilic aromatic substitution, and assuming the

thiophene ring of benzo[b]thiophene (shown) is activated toward electrophilic aromatic
substituted more so than the benzenoid ring, predict the preferential position of attack of
an electrophile, i.e., does the electrophile E+ attack carbon 2, or 3? Explain your
answer.
E
3
E+
(-H )
or
1
benzo[b]thiophene

Ans:
produces resonance forms without aromaticity
H
E
E
E+
S
-H
E+
E
S
-H+
S

152
167.

benzo[b] thiophene (shown).
E
3
2
S
E+
E
instead of
(-H+)
S
benzo[b]thiophene
Ans:
153

168.

benzo[b] furane (shown).
E
3
2
O
E+
instead of
(-H )
O
benzo[b]furan
Ans:
154

169.

indole (shown).
E
3
2
N
H
E+
instead of
(-H )
N
H
N
H
indole
Ans:
resonance stabilized through the nitrogen, without loss of the benzenoid ring aromaticity.
155

Section: 15.3, 15.10 and 15.11
170. When the following substance is treated with Br2/FeBr3, the major product is obtained in
good yield, and only very small amounts of minor products are found. What is this
major product and why are the minor products not formed to any significant degree?
Explain clearly.
O
Br2
FeBr3
HN
Ans: The major products are produced by brominating Ring B. Ring B is more
electron-rich due to the electron-donation of both the nitrogen and methyl groups
attached versus the two electron-withdrawing carbonyl groups attached to Ring A,
which make it inherently electron-poor. Therefore, bromination mainly occurs on
the more electron-rich benzene ring affording a mixture of the following two
compounds. Due to steric effects, bromination ortho to both the nitrogen and
methyl group would lead to a minor product. Also, because Ring A is electronpoor, bromination of this ring would also lead to minor products.
Ring
Ring
A
A
O
HN
Br
Ring
B
156
major products
HN
Br
Ring
B
Topic: Mechanism, Carbocation Stability

Section: 15.12
171. Acid-catalyzed hydration of 1-phenyl-1-pentene gives 1-phenyl-1-pentanol almost
exclusively; the other possible hydration product, 1-phenyl-2-pentanol, is not detected at
all. Explain clearly.
Ans: Acid catalyzed hydration of an alkene occurs through a carbocation intermediate.
Although 1-phenyl-1-pentene is symmetrically substituted at the C=C, the relative
stabilities of the two possible carbocation intermediates is significantly different:
although both are secondary carbocations, one is also benzylic and thus stabilized
by resonance. The observation that 1-phenyl-1-pentene gives 1-phenyl-1pentanol, almost exclusively, is in accordance with the general trend that acid
catalyzed hydration chiefly tends to afford products formed via the most stable
intermediate carbocation.
H3O+
H2O
+
H
2o, benzylic:
stabilized by
resonance,formed
2o, but not benzylic:

less stable, not
formed to any
almost exclusively
appreciable degree
OH
H
chief product
157
OH
not detected
Topic: EAS/non-EAS Reactivity

172. When toluene reacts with Cl2, the identity of the major product(s) obtained depends on
whether the reaction is carried out in the presence of catalytic amounts of FeCl3, or
without catalyst, at high temp. Explain clearly.
Ans: Reaction with Cl2/FeCl3 results in electrophilic aromatic substitution at the o- and
p- positions, since the methyl group in toluene is an activating, o-,p- director. In
contrast, when the reaction is carried out without catalyst, at high temperature, the
methyl group undergoes free-radical halogenation via the benzyl radical
intermediate.
Cl2
FeCl3
Cl
+
Cl
Cl
Cl2
heat
Section: 15.14
173. When two different groups are present on a benzene ring, the ____________ generally
determines the outcome of an EAS reaction.
Ans: more powerful activating group
174. Suggest a reasonable synthetic strategy for the synthesis of 3,5-dinitrobenzyl alcohol
from benzaldehyde.
NO2
NO2
Ans:
HNO3 (excess)
NaBH4
O
H2SO4
O H 2O
OH
O2 N
O2 N
heat
benzaldehyde
3,5-dinitrobenzyl alcohol
158

175. Suggest a reasonable synthetic strategy for the synthesis of 6-methyl-3-phenyl-3heptanol from 4-methylpentanoyl chloride, (CH3)2CHCH2CH2COCl
Ans:
O
OH
O
Cl
i) C2H5MgBr
ii) NH4Cl
AlCl3
4-methylpentanoyl chloride
6-methyl-3-phenyl-3-heptanol

1. Br2, FeBr3
2. Mg, ether
3. ethylene oxide
4. H3O+
5. PBr3
6. Mg, ether
7. O
8. H3O+, heat (-H2O

9. HF
Ans:
O
Br2, FeBr3
OH
MgBr
Br
Mg, ether
H3O+
PBr3
O
Br
MgBr
HF
Mg, ether
H3O+
(-H2O)
159

177. Propose a reasonable synthesis of the following compound from benzene.
multi-step process
Ans:
O
Br2, FeBr3
OH
MgBr
Br
Mg, ether
H3O+
PBr3
O
Br
MgBr
HF
Mg, ether
H3O+
(-H2O)
160

178. What product would result from the following series of reactions:
O
1. AlCl3
2. SOCl2
O
+
3. AlCl3
Ans:
O
O
SOCl2
AlCl3
COOH
AlCl3
COCl
O
161

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Explain the difference between electrophilic aromatic substitution and free radical halogenation of toluene.

Explain the difference between electrophilic aromatic substitution and free radical halogenation of toluene.

What is the major product of the reaction of toluene with chlorine in the presence of catalytic amounts of iron(III) chloride?

What is the major product of the reaction of toluene with chlorine in the presence of catalytic amounts of iron(III) chloride?

Chapter Fifteen

MULTIPLE CHOICE QUESTIONS

Topic: Functional Group Tests

Topic: Nomenclature, Functional Group Tests

Topic: Nomenclature, Reaction Products

Topic: Other EAS Considerations

Topic: Reaction Products

Topic: Reaction Products

Topic: Reaction Products

Topic: Reaction Products

Topic: Reaction Products

The reaction of benzene with

Topic: Reaction Products

Topic: Reaction Products

Topic: Reaction Products

Topic: Reaction Products

Topic: Reaction Products

Topic: Reaction Products

Topic: Reaction Products

Topic: Reaction Products

Topic: Directing Effects

Topic: Directing Effects

Topic: Directing Effects

Topic: Directing Effects

Topic: Directing Effects

Topic: Reaction Products

Topic: Reaction Products

Topic: Reaction Products

Topic: Reaction Products

Topic: Reaction Products

Topic: Reaction Products

Topic: Reaction Products

Topic: Reaction Products

Topic: Reaction Products

Topic: Reaction Products

Topic: Reaction Products

Topic: Reaction Products

Topic: Reaction Products

Topic: Reaction Products

Topic: Reaction Products

Topic: Reaction Products

Topic: Reaction Products

Topic: Reaction Products

Topic: Reaction Products

Topic: Reaction Products

Topic: Reaction Products

Topic: Reaction Products

Topic: Reaction Products

Topic: Reaction Products

Topic: Relative Reactivities

Topic: Relative Reactivities

Topic: Relative Reactivities

Topic: Relative Reactivities

Topic: Relative Reactivities