Chapter 15 - Test Bank Chem 200

Package Title: Solomons Test Bank
Course Title: Solomons 11e

Chapter Number: 15
Question Type: Multiple Choice
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
Answer: D
Topic: Mechanisms and Intermediates
Section: 15.2
Difficulty Level: Medium
2) Which of these is the rate-determining step in the sulfonation of benzene?

a) Formation of SO3 from sulfuric acid
b) Protonation of SO3 sulfuric acid
c) Addition of SO3H+ to benzene to form the arenium ion
d) Loss of a proton from the arenium ion to form benzenesulfonic acid
e) None of these choices.
Answer: C
Section: 15.2
3) Which of these is the rate-determining step in the bromination of benzene?

a) Complexation of bromine with the iron(III) bromide catalyst
b) Formation of Br+ ion
c) Addition of Br+ to benzene to form the arenium ion
d) Loss of a proton from the arenium ion to form bromobenzene
Answer: C
Section: 15.2
4) 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) I
b) II
c) III
d) IV
e) All of these choices.
Answer: E
Section: 15.11
formed when chlorobenzene undergoes para-chlorination?
..
..
..
..
: Cl :
: Cl +
: Cl :
: Cl :
+
+
+
H Cl
H Cl
H Cl
H Cl
II
III
IV
a) I
b) II
c) III
d) IV
Answer: E
2
Section: 15.11
formed when acetanilide undergoes para-bromination?
+NCOCH
:NHCOCH3
: NHCOCH3
: NHCOCH3
3
+
+
+
H Br
H Br
H Br
H Br
II
III
IV
a) I
b) II
c) III
d) IV
Answer: E
Section: 15.11
7) 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) I
b) II
c) III
d) IV
Answer: B
Section: 15.11
8) Consider the structures given below. Which of them would be a relatively stable contributor
to the hybrid formed when toluene undergoes para bromination?
a) I
b) II
c) III
d) IV
e) V
Answer: C
Section: 15.11
9) 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
H
Cl
+H
H
Cl
II
Cl
III
a) I
b) II
c) III
d) None of these contribute.
e) All of these contribute.
Answer: E
Section: 15.11
10) Consider the resonance forms shown for the arenium ionformed from the bromination of
acetanilide. Which resonance form contributes most to the overall resonance hybrid?
4
H
I
Br
HN
HN
HN
Br
H
II
Br
HN
Br
IV
III
a) I
b) II
c) III
d) IV
e) All contribute equally.
Answer: C
Section: 15.11
11) Consider the resonance forms shown for the arenium ionformed from the bromination of
acetanilide. Which resonance form contributes most to the overall resonance hybrid?
a) I
b) II
c) III
d) IV
e) All contribute equally.
Answer: D
5

Section: 15.11
12) 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.
Answer: C
Topic: Other EAS Considerations
Section: 15.3
Difficulty Level: Easy
13) 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.
Answer: C
Section: 15.2
14) 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 of these choices could be used.
Answer: A

Section: 15.8
15) 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
Answer: A
Section: 15.8
16) 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
Answer: C
Section: 15.10 and 15.11
17) 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
Answer: C
7

Section: 15.8
18) 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
Answer: D
Section: 15.8
19) Which one of these molecules can be a reactant in a Friedel-Crafts reaction?

a) Aniline
b) Benzenesulfonic acid
c) Chloroethene
d) Bromobenzene
e) p-Bromonitrobenzene
Answer: D
Section: 15.8
20) 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
Answer: B
8
Topic: Functional Group Tests

Sections: 14.2, 14.3 and 15.3
21) 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
Answer: C
Topic: Nomenclature, Functional Group Tests
Section: 14.2, 14.11 and 15.3
22) 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
Answer: B
Topic: Nomenclature, Reaction Products
Difficulty Level: Hard
23) 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
Answer: B
24) 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
Answer: D
Section: 14.2, 15.3, and 15.8
25) A mixture of chlorobenzene (1 mol) and anisole (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
d) 4-bromoanisole
e) 3-bromoanisole
Answer: D
Section: 14.2, 15.3, and 15.8
26) Which of the following reactions could be used to synthesize tert-butylbenzene?

a) C6H6 + CH2=C(CH3)2
H2SO4
10
b) C6H6 + (CH3)3COH
c) C6H6 + (CH3)3CCl
d) All of these choices.
H2SO4
AlCl3
Answer: D
Topic: Synthesis
Section: 15.6

a) C6H6 + CH2=C(CH3)2
H2SO4
b)
c) C6H6 + (CH3)3CCl
AlCl3
Answer: D
Topic: Synthesis
Section: 15.6
a)
b)
c) C6H6 + (CH3)3CCl
AlCl3
Answer: D
Topic: Synthesis
11
Section: 15.6
29) Consider the following reaction: what is the expected product?

NH2
Br2, H2O
Cl
Cl
NH2
Br
Br
H2 N
Cl
Br
Br
Cl
NH2
II
Br
Br
III
NH2
NH2
Br
Br
Br
Cl
Cl
IV
a) I
b) II
c) III
d) IV
e) V
Answer: B
Topic: Synthesis
Section: 15.3
30) Which of the following reactions would yield isopropylbenzene as the major product?
CH3CHCH3
Benzene
b)
OH
H2SO4
CH3CHCH3
Benzene
c)
Cl
AlCl3
12
Benzene
CH3CH2CH2Cl
AlCl3
d)
Answer: E
Topic: Synthesis
Section: 15.6
a)
CH3CHCH3
Benzene
b)
OH
H2SO4
CH3CHCH3
Benzene
c)
Cl
AlCl3
CH3CH2CH2Cl
Benzene
AlCl3
d)
Answer: E
Topic: Synthesis
Section: 15.6
a)
13
b)
CH3CHCH3
Benzene
c)
Benzene
Cl
AlCl3
CH3CH2CH2Cl
AlCl3
d)
Answer: E
Topic: Synthesis
Section: 15.6
33) Which of the following reactions would produce isopropylbenzene?

Cl
Benzene
a)
Benzene
b)
AlCl3
HF
OH
Benzene
H2SO4
c)
Br
Benzene
AlCl3
d)
Answer: E
Topic: Synthesis
Section: 15.6
34) Which of these is a satisfactory synthesis of 1-chloro-2-phenylethane?

14
a) C6H5CH2CH3 + Cl2, Fe
b) C6H5CH2CH3 + Cl2, 400C
c) C6H5CH2CH2OH + SOCl2
d) C6H5CH=CH2 + HCl, peroxide
e) C6H6 + CH3CH2Cl, AlCl3
Answer: C
Topic: Synthesis
Sections: 11.9 and 15.6
35) 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
Answer: C
Topic: Synthesis
Sections: 11.9 and 15.6
36) Which of the following reactions would produce cumene?

Cl
Benzene
a)
Benzene
b)
AlCl3
HF
OH
Benzene
H2SO4
c)
Br
Benzene
AlCl3
d)
Answer: E
15
Topic: Synthesis
Section: 15.6
37) Which of the following reactions would yield cumene as the major product?
Benzene
a)
CH3CH
CH2
H2SO4
CH3CHCH3
Benzene
b)
OH
H2SO4
CH3CHCH3
Benzene
c)
Benzene
Cl
AlCl3
CH3CH2CH2Cl
AlCl3
d)
Answer: E
Topic: Synthesis
Section: 15.6
38) Which of the following reactions would give the product(s) indicated in substantial amounts
(i.e., in greater than 50% yield)?
NH2
NH2
+ CH3Cl
AlCl3
NH2
and
CH3
CH3
NH2
II
NH2
+ CH3Cl
AlCl3
CH3
III
+ CH3CH2CH2Cl
CH2CH2CH3
AlCl3
16
a) I
b) II
c) III
Answer: E
Topic: Reaction Products
39) What would you expect to be the major product obtained from the following reaction?
O
excess
HN
AlCl3
CH3Cl
HN
HN
HN
II
III
HN
HN
IV
a) I
b) II
c) III
d) IV
e) V
Answer: E
17
O2N
AlCl3
O2 N
O
II
O2N
O2N
O2N
O
Cl
III
O2 N
IV
a) I
b) II
c) III
d) IV
e) V
Answer: A
41) The major product(s) of the following reaction,
18
O
O
AlCl3
Cl
O
O
O
O
I
O
II
III
O
IV
V
O
would be:
a) I
b) II
c) III
d) IV
e) V
Answer: E
42) What might be predicted to happen when the following substance undergoes Friedel-Crafts
acylation?
O2N
CH2
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 these choices. No reaction will occur.
Answer: A
19

43) 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
III
a) I
b) II
c) III
d) IV
e) V
Answer: E
20
OH
i) SOCl 2
ii) C6H6, AlCl3
iii) H2NNH2/KOH
OH
OH
II
III
IV
a) I
b) II
c) III
d) IV
e) V
Answer: E

OH
O
i) PCl5
ii) C6H6, AlCl3
OH
O
OH
II
IV
III
a) I
21
b) II
c) III
d) IV
e) V
Answer: E
a) I
b) II
c) III
d) IV
e) V
Answer: E
22
OH
i) SOCl2
ii) C6H6, AlCl3
OH
II
III
O
OH
IV
a) I
b) II
c) III
d) IV
e) V
Answer: B
23
a) I
b) II
c) III
d) IV
e) V
Answer: B
49) 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
24
a) I
b) II
c) III
d) IV
e) V
Answer: C
a) I
b) II
c) III
d) IV
e) V
Answer: C
25
O
OH
i) PCl5
ii) benzene, AlCl3
iii) Zn(Hg), HCl
SO2
CO2
CH2
II
III
IV
a) I
b) II
c) III
d) IV
e) V
Answer: C
a) I
b) II
c) III
d) IV
26
e) V
Answer: C
53) 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) I
b) II
c) III
d) IV
e) V
Answer: C
54) Which would be the product, X, of the following reaction sequence?
27
a) I
b) II
c) III
d) IV
e) V
Answer: C
55) The major product(s), D, of the following reaction,
28
O
C CH2
Br
Br2
FeBr3
C CH2
C CH2
Br
II
C CH2
C CH2
Br
Br
III
IV
would be:
a) I
b) II
c) III
d) IV
e) Approximately equal amounts of I and II.
Answer: D
56) The major product, D, of the following reaction,
29
O
H2SO4
SO3
HO3S
II
I
SO3H
SO3H
SO3H
IV
III
O
SO3H
would be:
a) I
b) II
c) III
d) IV
e) V
Answer: D
30
COOH
SO3H
COOH
Br
Br2
FeBr3
COOH
COOH
COOH
Br
SO3H
SO3H
Br
SO3H
SO3H
Br
II
III
IV
a) I
b) II
c) III
d) IV
e) Equal amounts of II and IV.
Answer: C
NO2
Br2
NO2
FeBr3
SO3H
NO2
NO2
NO2
Br
Br
SO3H
SO3H
Br
SO3H
SO3H
Br
II
III
IV
a) I
b) II
c) III
d) IV
Answer: C
31
O
Br2, FeBr3
Br
O
Br
Br
II
III
Br
O
Br
IV
a) I
b) II
c) III
d) IV
e) V
Answer: D
32
1 equiv. Br2
FeBr3
Br
Br
II
Br
III
Br
Br
IV
a) I
b) II
c) III
d) IV
e) V
Answer: C
33
1 equiv. Cl2
FeCl3
Cl
Cl
Cl
II
III
Cl
Cl
IV
a) I
b) II
c) III
d) IV
e) V
Answer: C
O
Cl2, FeCl3
HN
Cl
O
HN
HN
II
III
Cl
HN
Cl
I
O
HN
HN
Cl
Cl
IV
34
a) I
b) II
c) III
d) IV
e) V
Answer: E
1 equivalent Br2
O
FeBr3
Br
O
Br
III
II
Br
O
O
Br
IV
a) I
b) II
c) III
d) IV
e) V
Answer: C
35
Br
64) What would you expect to be the major product obtained from the monobromination of mdichlorobenzene?
Cl
Cl
Cl
Br
Cl
Cl
Br
Br
II
Cl
III
a) I
b) II
c) III
d) Equal amounts of I and II.
e) Equal amounts of I, II and III.
Answer: B
65) Which would be the major product(s) of the following reaction?

H3CO
Br2, FeBr3
H3CO
H3CO
H3CO
Br
Br
Br2Fe
II
III
a) I
b) II
c) III
d) I and II in roughly equal amounts.
e) I and III in roughly equal amounts.
Answer: A
36
O
HNO3
H2SO4, heat
HN
O
O2N
HN
NO2
O
HN
HN
II
III
O2N
I
O
HN
HN
IV
NO2
NO2
a) I
b) II
c) III
d) IV
e) V
Answer: E
37
HNO3
H2SO4, heat
O 2N
O
O2 N
II
III
NO2
O
O
O
NO2
IV
a) I
b) II
c) III
d) IV
e) V
Answer: C
68) What would be the major product(s) of the following reaction?

CO2H
HNO3
H2SO4, heat
NO2
CO2H
NO2
NO2
CO2H
NO2
NO2
II
CO2H
O2N
O2N
CO2H
NO2
NO2
IV
III
a) I
b) II
c) III
38
NO2
d) IV
e) Approximately equal amounts of II and IV.
Answer: C
1 equiv. HNO3
H2SO4, heat
O 2N
NO2
II
NO2
III
NO2
O2N
IV
a) I
b) II
c) III
d) IV
e) V
Answer: C
39
HNO3
H2SO4, heat
HN
O2N
HN
HN
HN
NO2
O2N
II
III
NO2
HN
HN
NO2
IV
a) I
b) II
c) III
d) IV
e) V
Answer: A
71) What would you expect to be the major product(s) obtained from the mononitration of mdichlorobenzene?
Cl
Cl
Cl
NO2
Cl
Cl
NO2
O2N
II
Cl
III
a) I
b) II
c) III
d) Equal amounts of I and II.
e) Equal amounts of I, II and III.
Answer: B
40

72) 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
O2N
SO3H
O2N
NO2
II
SO3H
SO3H
IV
III
a) I
b) II
c) III
d) IV
e) Equal amounts of I and II.
Answer: C
73) The major product(s), D, of the following reaction
41
HNO3
H2SO4
O
O2N
NO2
II
NO2
O
NO2
IV
III
would be:
a) I
b) II
c) III
d) IV
e) Equal amounts of I and II.
Answer: D

HO
HNO3
H2SO4
HO
HO
HO
NO2
NO2
HO3S
II
III
a) I
b) II
c) III
42

Answer: A

H3CO
HNO3
H2SO4
H3CO
H3CO
H3CO
NO2
NO2
HO3S
II
III
a) I
b) II
c) III
Answer: A
43
H2SO4
NO2
O
O
HO3S
SO3H
NO2
NO2
SO3H
HO3S
II
NO2
NO2
IV
III
a) I
b) II
c) III
d) Equal amounts of I and IV.
Answer: C

O
H2SO4
NO2
SO3
O
O
HO3S
SO3H
NO2
NO2
SO3H
II
HO3S
NO2
NO2
IV
III
a) I
b) II
c) III
d) Equal amounts of I and IV.
Answer: C
44

78) The major product(s), C, of the following reaction,

Cl
Cl
Cl
SO3
H2SO4
Cl
Cl
SO3H
Cl
Cl
SO3H
HO3S
II
Cl
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.
Answer: B
79) The major product(s), A, of the following reaction,

Cl2, h
CH3CH2
CH3CH2
400 - 600 oC
Cl
CH3CH2
ClCH2CH2
CH3CH
Cl
Cl
II
III
IV
would be:
45
a) I
b) II
c) A mixture of I and II.
d) III
e) IV
Answer: E
Section: 15.12

excess Cl2
400o - 600oC
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
II
IV
III
a) I
b) II
d) III
e) IV
Answer: A
Section: 15.12
46
excess NBS
?
ROOR
Br
Br
Br
Br
Br
Br
Br
Br
II
IV
III
a) I
b) II
d) III
e) IV
Answer: D
Section: 15.12

NBS
?
ROOR
Br
Br
Br
Br
II
III
would be:
a) I
b) II
47
IV
d) III
e) IV
Answer: E
Section: 15.12
83) What would be the major product of the following reaction?

Cl2
CH2CH2CH3
Cl
CH2CH2CH3
400 oC
CH2CH2CH3
CHCH2CH3
Cl
Cl
II
CH2CHCH3
III
CH2CH2CH2Cl
Cl
IV
a) I
b) II
c) III
d) IV
e) V
Answer: C
Section: 15.12
48
NBS
?
ROOR
Br
Br
Br
Br
Br
III
II
IV
a) I
b) II
c) III
d) IV
e) V
Answer: D
Section: 15.12

excess NBS
?
ROOR
Br
Br
Br
Br
Br
Br
Br
Br
III
II
Br
IV
Br
IV
49
a) I
b) II
c) III
d) IV
e) V
Answer: C
Section: 15.12
Cl2
peroxides
Cl
Cl
II
Cl
III
Cl
Cl
IV
a) I
b) II
c) III
d) IV
e) V
Answer: E
Section: 15.12
50
Cl2
light
Cl
Cl
Cl
II
III
Cl
Cl
IV
a) I
b) II
c) III
d) IV
e) V
Answer: E
Section: 15.12

NBS, ROOR
?
light
Br
Br
Br
II
III
Br
Br
IV
a) I
b) II
51
c) III
d) IV
e) V
Answer: C
Section: 15.12
89) When toluene is reacted in turn with 1) Cl2 (large excess), heat, and light and 2) Br2,FeBr3,
the chief product is:
Br
CCl3
CCl3
Br
CCl3
Br
Cl
Br
II
III
IV
a) I
b) II
c) III
d) IV
e) A mixture of III and IV.
Answer: B
52
HNO3
H2SO4, heat
N
N
O2N
N
N
NO2
O
N
O 2N
II
III
O
O
N
N
NO2
NO2
IV
a) I
b) II
c) III
d) IV
e) V
Answer: E
53
N=O
Br2
FeBr3
N=O
N=O
N=O
Br
Br
Br
I
II
III
N-OBr
Br
IV
a) I
b) II
c) III
d) IV
e) A mixture of II and III.
Answer: E
92) The reaction of benzene with (CH3)3CCH2Cl in the presence of anhydrous aluminum
chloride produces principally which of these?
54
II
III
IV
a) I
b) II
c) III
d) IV
e) V
Answer: E
93) The reaction of benzene with

Cl
in the presence of anhydrous aluminum
II
IV
III
a) I
b) II
c) III
55
d) IV
e) V
Answer: D

in the presence of anhydrous aluminum
II
IV
III
a) I
b) II
c) III
d) IV
e) V
Answer: D
56
Cl

produces principally which of these?
in the presence of anhydrous aluminum chloride
II
IV
III
a) I
b) II
c) III
d) IV
e) V
Answer: A

produces principally which of these?
in the presence of anhydrous aluminum chloride
57
a) I
b) II
c) III
d) IV
e) V
Answer: A
97) 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?
58
CO2H
Br
CO2H
CO2H
NO2
Br
NO2
NO2
Br
II
III
Br
CH3
NO2
Br
NO2
CO2H
IV
a) I
b) II
c) III
d) IV
e) V
Answer: A
Section: 15.3, 15.4, 15.10, and 15.13
98) 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?
a) I
b) II
c) III
d) IV
59
e) V
Answer: D
Section: 15.3, 15.4, 15.10, and 15.13
99) 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
III
HO
HO
IV
a) I
b) II
c) III
d) IV
e) V
Answer: D
Topic: Reaction products
Section: 15.6, 15.12, 15.13
60
i) HF
iv) m-CPBA
v) CH3MgBr
vi) NH4Cl
Br
HO
HO
II
III
HO
HO
IV
a) I
b) II
c) III
d) IV
e) V
Answer: D
Section: 15.6, 15.12, 15.13
61
i) BF3
iv) m-CPBA
v) CH3MgBr
vi) NH4Cl
OH
Br
HO
HO
II
III
HO
HO
IV
a) I
b) II
c) III
d) IV
e) V
Answer: D
Section: 15.6, 15.12, 15.13
102) 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
Answer: A
Topic: Directing Effects
Section: 15.10
62
103) Which of the following is not a meta-directing substituent when present on the benzene
ring?
a) -N=O
b) -NO2
c) -N(CH3)3+
d) -CN
e) -CO2H
Answer: A
Section: 15.10
104) 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.
Cl
COOH
Cl
NHCOCH3
CCH3
Cl
NO2
OH
II
III
CH3
CH2CH3
IV
a) I
b) II
c) III
d) IV
e) V
Answer: C
Section: 15.14
105) Which of the following compounds would yield the greatest amount of meta product when
subjected to ring nitration?
63
HO
O
HO
O
HO
HO
OH
II
IV
III
a) I
b) II
c) III
d) IV
e) V
Answer: A
Section: 15.10
106) Which of the following is not an ortho-para director in electrophilic aromatic substitution?
a) -CF3
b) -OCH3
c) -CH3
d) -F
e) -NH2
Answer: A
Section: 15.10
a) -CCl3
b) -OCH3
c) -CH3
d) -F
e) -NH2
Answer: A
64

Section: 15.10
a) -SO3H
b) -OCH3
c) -CH3
d) -F
e) -NH2
Answer: A
Section: 15.10
a)
b) -OCH3
c) -CH3
d) -F
e) -NH2
Answer: A
Section: 15.10
110) 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
Answer: E
65

Section: 15.10
111) (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.
Answer: D
Section: 15.10
112) 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.
Answer: A
113) Which of these compounds gives essentially a single product on electrophilic substitution of
a third group?
a) p-chlorotoluene
b) m-ethylanisole
d) m-xylene
e) 3-hydroxybenzoic acid
Answer: D
66

Section: 15.10
114) Arrange the following compounds in order of decreasing reactivity in electrophilic

substitution:
O
Br
II
III
NO2
IV
a) V > II > I > III > IV

b) II > V > III > I > IV
c) IV > I > III > V > II
d) III > II > I > IV > V
e) IV > V > II > I > III
Answer: B
Section: 15.10
115) 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 must possess 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.
Answer: C
Section: 15.11
116) The ortho/para product ratio is expected to be the smallest for the bromination of which of
these?
a) Toluene
b) Isopropylbenzene
c) Butylbenzene
67
d) sec-Butylbenzene
e) tert-Butylbenzene
Answer: E
117) 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
Answer: B
Topic: Reagents
ethylbenzene 2- and 4-chloro-1-ethylbenzene
b) Cl2, FeCl3
c) SOCl2
d) C2H5Cl, AlCl3
Answer: B
Topic: Reagents
t-butylbenzene p-chloro substitution product
68
b) Cl2, FeCl3
c) SOCl2
d) C2H5Cl, AlCl3
e) HCl, peroxide
Answer: B
Topic: Reagents
ethylbenzene 1-chloro-1-phenylethane
a) Cl2, light, or heat
b) Cl2, FeCl3
c) SOCl2
d) C2H5Cl, AlCl3
e) HCl, O2
Answer: A
Topic: Reagents
Section: 15.12
121) 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
Answer: C
Topic: Reagents
122) Which reagent would you use to carry out the following transformation?
tert-butylbenzene p-tert-butylbenzenesulfonic acid
69
+
o-tert-butylbenzenesulfonic acid
a) HNO3/H2SO4
b) tert-C4H9Cl/AlCl3
c) H2SO3/peroxides
d) SO3/H2SO4
e) SO2/H2SO3
Answer: D
Topic: Reagents
toluene benzoic acid
a) Br2, heat, and light
b) Cl2, FeCl3
c) KMnO4, OH-, heat (then H3O+)
d) HNO3/H2SO4
e) SO3/H2SO4
Answer: C
Topic: Reagents
Section: 15.13
ethylbenzene benzoic acid
b) Cl2, FeCl3
c) KMnO4, OH-, heat (then H3O+)
d) HNO3/H2SO4
e) SO3/H2SO4
Answer: C
Topic: Reagents
Section: 15.13
70
cumene 2- and 4-chlorocumene
b) Cl2, FeCl3
c) SOCl2
d) C2H5Cl, AlCl3
e) HCl, peroxides
Answer: B
Topic: Reagents
toluene benzyl bromide
a) Br2, FeBr3
b) N-Bromosuccinimide, ROOR, h
c) HBr
d) Br2/CCl4
e) NaBr, H2SO4
Answer: B
Topic: Reagents
Section: 15.12
127) 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
1) CH3CH2CCl , AlCl3 2) Br2, Fe 3) Zn(Hg), HCl
c)
1) CH3CH2CCl , AlCl3
2) Zn(Hg), HCl
3) Br2, Fe
O
d)
e) (1) (CH3)2CHCl, AlCl3 (2) Br2,Fe
71
Answer: D
Topic: Reagents
Section: 15.14
128) 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
1) CH3CH2CCl , AlCl3 2) Br2, Fe 3) Zn(Hg), HCl
O
c)
d)
e) (1) (CH3)2CHCl, AlCl3 (2) Br2,Fe
Answer: D
Topic: Reagents
Section: 15.14
129) Which of the following compounds would be most reactive toward electrophilic
substitution?
OH
CH3
II
Br
III
a) I
b) II
c) III
d) IV
e) V
Answer: A
Topic: Relative Reactivities
Section: 15.11
72
CHO
NO2
IV
130) Which of the following compounds would be least reactive toward electrophilic
substitution?
OH
CH3
II
Br
III
CHO
NO2
IV
a) I
b) II
c) III
d) IV
e) V
Answer: E
Section: 15.11
131) Which of the following compounds would be most reactive to ring bromination?
CH3
NO2
II
CF3
III
Cl
NH2
IV
a) I
b) II
c) III
d) IV
e) V
Answer: E
Section: 15.11
132) Which of the following compounds would be least reactive toward electrophilic
substitution?
73
O
O
NO2
NH
NO2
II
IV
III
a) I
b) II
c) III
d) IV
e) V
Answer: B
Section: 15.11
133) Which of the following compounds would be most reactive toward electrophilic
substitution?
O
O
NO2
NH
NH2
NO2
II
IV
III
a) I
b) II
c) III
d) IV
e) V
Answer: E
Section: 15.11
134) Which of the following compounds would be most reactive toward ring nitration?
74
O
O
I
a) I
b) II
c) III
d) IV
e) V
II
CF3
III
OH
NH
IV
Answer: D
Section: 15.11
135) Which of the compounds listed below would you expect to give the greatest amount of
meta-product when subjected to ring bromination?
OH
HO
II
NH2
III
OCH3
CH3
IV
a) I
b) II
c) III
d) IV
e) V
Answer: B
Section: 15.11
136) Which of the following compounds would be most reactive toward ring bromination?
75
O
O
HO
NH2
OCH3
II
IV
III
a) I
b) II
c) III
d) IV
e) V
Answer: C
Section: 15.11
137) Which of the compounds listed below would you expect to give the greatest amount of
meta-product when subjected to ring nitration?
O
II
NH
III
OCH3
CH3
IV
a) I
b) II
c) III
d) IV
e) V
Answer: B
Section: 15.11
138) Which of the following compounds would you expect to be most reactive toward ring
nitration?
a) Benzene
b) Toluene
76
c) m-Xylene
d) p-Xylene
e) Benzoic acid
Answer: C
Section: 15.11
139) 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
Answer: C
Section: 15.11
140.)Which of the following structures would not be a contributor to the resonance hybrid of the
benzyl cation?
CH3
H
H
+
I
CH3
+CH2
CH2
CH3
+
II
III
IV
a) I
b) II
c) III
d) IV
e) V
Answer: A
Topic: Non-EAS Relative Rates and Intermediates
Section: 15.12
77
IV
141) Which of the following carbocations would be most stable?

CH3
a) C6H5CH2CH2CHCH2
CH2
b) C6H5CH2CH2CHCH3
CH3
C6H5CH2CH2CCH3
c)
CH3
d) C6H5CH2CHCHCH3
CH3
e) C6H5CHCH2CHCH3
Answer: E
Section: 15.12
142) Which alkyl halide would be most reactive in an SN2 reaction?

a) C6H5CH2CH2CH2Br
C6H5CHCH2Br
b)
CH3
C6H5CH2CHCH3
Br
c)
CH3
C6H5CCH2Br
d)
CH3
Br
C6H5CCH3
e)
CH3
78
Answer: A
Section: 15.15
143) Which alkyl halide would be most reactive in an SN1 reaction?

a) C6H5CH2CH2CH2Br
C6H5CH2CHCH3
Br
CH3
b)
C6H5CH2CBr
CH3
c)
Br
C6H5CCH3
d)
CH3
CH3
C6H5CCH2Br
e)
CH3
Answer: D
Section: 15.15
144) The rate of solvolysis in ethanol is least for which of these compounds?
a) C6H5CH2Cl
C6H5C(CH3)2
Cl
b)
c) (C6H5)2CHCl
C6H5CHCl
CH3
d)
e) (C6H5)3CCl
Answer: A
79

Section: 15.15
145) 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) Two of these choices.
Answer: E
Section: 15.16
146) 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
Answer: E
Topic: Synthesis
Section: 15.13
147) Benzoic acid can be prepared by the oxidation of which of the following compounds:
a) C6H5CH=CH2
b) C6H5CCH
c) C6H5COCH3
d) C6H5CH2CH2CH3
80
Answer: E
Topic: Synthesis
Section: 15.13
148) Benzoic acid can be prepared by the oxidation of which of the following compounds:
a) C6H5CH=CH2
b) C6H5CCH
c) C6H5COCH3
d) C6H5CH(CH3)2
Answer: E
Topic: Synthesis
Section: 15.13
149) 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
Answer: D
Topic: Synthesis
Section: 15.13
150) What reagent can effect the following transformation?

Br
CO2H
Br
Br
CO2H
Br
CO2H
a) CO2; then H3O+

b) H3O+, heat
c) Mg; then CO2; then H3O+
81
d) H2O2, heat
e) KMnO4, OH-, heat; then H3O+
Answer: E
Topic: Synthesis
Section: 15.13
151) A good synthesis of

O
(CH3)3C
CCH3
would be:
O
Benzene
a)
CH3CCl
(CH3)3CCl
AlCl3
AlCl3
O
Benzene
b)
(CH3)3CCl
CH3CCl
AlCl3
AlCl3
Benzene
CH3CCl
(CH3)2C
CH2
AlCl3
HF
c)
d) More than one of these choices.
Answer: B
Topic: Synthesis
Section: 15.14
152) Which would be a good synthesis of m-nitrobenzoic acid?

Benzene
a)
HNO3/H2SO4
CH3Cl
1. KMnO4, NaOH, heat
heat
AlCl3
2. H3O+
82
Toluene
b)
Toluene
HNO3/H2SO4
2. H3O+
heat
HNO3/H2SO4
2. H3O+
c)
d) More than one of these choices.
heat
Answer: C
Topic: Synthesis
Section: 15.14
153) Which of the following would be the best synthesis of 1,4-dimethyl-2-nitrobenzene?

Benzene
a)
Toluene
b)
p-Xylene
HNO3
H2SO4
HNO3
product
2 CH3Cl
2 AlCl3
product
H2SO4
HNO3
CH3Cl
AlCl3
H2SO4
CH3Cl
m-Nitrotoluene
AlCl3
d)
e) All of these choices are equally good.
c)
Answer: C
Topic: Nomenclature, Synthesis
Section: 15.14
154) 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.
83
d) HNO3/H2SO4; then KMnO4/-OH/heat, followed by H3O+; then CH3Cl/AlCl3.

e) HNO3/H2SO4; then CO2, followed by H3O+.
Answer: B
Topic: Synthesis
Section: 15.14
155) 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+.
Answer: C
Topic: Synthesis
Section: 15.14
156) How might the following synthesis be carried out:

CH2CH3
Benzene
C 6 H6
a)
C 6 H6
b)
several
steps
CH3CH2Cl
AlCl3
Cl2
FeCl3
Cl
Cl2
FeCl3
CH3CH2Cl
AlCl3
product
product
C6H6
c)
CH3CCl
Cl2
Zn(Hg)
AlCl3
FeCl3
HCl
CH3CCl
Zn(Hg)
Cl2
AlCl3
HCl
FeCl3
product
C6H6
d)
84
product
e) None of these syntheses is satisfactory.

Answer: C
Topic: Synthesis
Section: 15.14

CH2CH3
Benzene
C 6 H6
a)
C 6 H6
b)
several
steps
CH3CH2Cl
Cl
Cl2
FeCl3
CH3CH2Cl
AlCl3
Cl2
FeCl3
AlCl3
product
product
C6H6
c)
CH3CCl
Cl2
H2NNH2
AlCl3
FeCl3
KOH
product
C6H6
CH3CCl
Zn(Hg)
Cl2
AlCl3
HCl
FeCl3
d)
Answer: C
Topic: Synthesis
Section: 15.14

several
steps
Cl
85
product
C 6 H6
a)
C 6 H6
b)
CH3CH2Cl
Cl2
AlCl3
Cl2
FeCl3
CH3CH2Cl
FeCl3
AlCl3
product
product
C6H6
c)
CH3CCl
Cl2
Zn(Hg)
AlCl3
FeCl3
HCl
CH3CCl
Zn(Hg)
Cl2
AlCl3
HCl
FeCl3
product
C6H6
d)
product
Answer: D
Topic: Synthesis
Section: 15.14

several
steps
Cl
C 6 H6
a)
C 6 H6
b)
CH3CH2Cl
AlCl3
Cl2
FeCl3
Cl2
FeCl3
CH3CH2Cl
AlCl3
product
product
C6H6
c)
CH3CCl
Cl2
Zn(Hg)
AlCl3
FeCl3
HCl
product
C6H6
CH3CCl
H2NNH2
Cl2
KOH
FeCl3
product
AlCl3
d)
86
Answer: D
Topic: Synthesis
Section: 15.14

several
steps
Cl
C 6 H6
a)
C 6 H6
b)
CH3CH2Cl
Cl2
AlCl3
Cl2
FeCl3
CH3CH2Cl
FeCl3
AlCl3
product
product
C6H6
c)
CH3CCl
Cl2
H2NNH2
AlCl3
FeCl3
KOH
product
C6H6
H2NNH2
CH3CCl
Cl2
product
KOH
FeCl3
AlCl3
d)
Answer: D
Topic: Synthesis
Section: 15.14
161) Which is the best sequence of reactions for the preparation of p-bromostyrene from
ethylbenzene?
ethylbenzene
a)
NBS, h
Br2
KOH
CCl4
Fe
CH3CH2OH
87
product
ethylbenzene
Br2
NBS, h
KOH
Fe
CCl4
CH3CH2OH
b)
ethylbenzene
NBS, h
KOH
Br2
CCl4
ZnO
CH3CH2OH
c)
Br2
product
ethylbenzene
Fe
630 oC
d)
product
product
Fe
Answer: B
Topic: Synthesis
Section: 15.14
162) Which is the best sequence of reactions for the following transformation?
O
NO2
a) i) HNO3, H2SO4; ii) CH3MgBr, Et2O; iii) H3O+, heat

b) i) CH3MgBr, Et2O; ii) H3O+, heat; iii) HNO3, H2SO4
c) i) HNO3, H2SO4; ii) NaBH4, H2O; iii) H3O+, heat
d) i) HNO3, H2SO4; ii) LiAlH4, H2O; iii) H3O+, heat
Answer: A
Topic: Synthesis
Section: 15.14
O
OH
NO2
a) i) HNO3, H2SO4; ii) CH3MgBr, Et2O; iii) H2O, NH4Cl

88

Answer: A
Topic: Synthesis
Section: 15.14
O
OH
NO2
a) i) HNO3, H2SO4; ii) CH3MgBr, Et2O; iii) H2O, NH4Cl

Answer: A
Topic: Synthesis
Section: 15.14
O
NO2
a) i) HNO3, H2SO4; ii) CH3MgBr, Et2O; iii) H3O+, heat

d) i)HNO3, H2SO4; ii) LiAlH4, H2O; iii) H3O+, heat
89

Answer: A
Topic: Synthesis
Section: 15.14
OH
O
OCH3
NO2
a) i) HNO3, H2SO4; ii) 2EtMgBr, Et2O; iii) NH4Cl

b) i) 2EtMgBr, Et2O; ii) H3O+; iii) HNO3, H2SO4
c) i) HNO3, H2SO4; ii) NaBH4, H2O; iii) 2EtMgBr, Et2O
d) i) LAH; ii) 2EtLi, Et2O; iii) HNO3, H2SO4, heat
Answer: A
Topic: Synthesis
Section: 15.14
O
OCH3
NO2
NO2
a) i) HNO3, H2SO4; ii) 2EtMgBr, Et2O; iii) NH4Cl

b) i) 2EtMgBr, Et2O; ii) H3O+; iii) HNO3, H2SO4
c) i) HNO3, H2SO4; ii) NaBH4, H2O; iii) 2EtMgBr, Et2O
d) i) LAH; ii) 2EtLi, Et2O; iii) HNO3, H2SO4, heat
Answer: A
Topic: Synthesis
90
Section: 15.14
O
OH
NO2
a) i) SOCl2; ii) C6H6, AlCl3; iii) Zn(Hg),HCl; iv) HNO3, H2SO4

b) i) SOCl2; ii) HNO3, H2SO4; iii) C6H6, AlCl3; iv) H2, Ni
c) i) HNO3, H2SO4; ii) SOCl2; iii) C6H6, AlCl3; iv) Zn(Hg),HCl
d) i) PBr3; ii) HNO3, H2SO4; iii) C6H6, AlCl3; iv) NaBH4, H2O
e) Two of these syntheses are satisfactory.
Answer: C
Topic: Synthesis
Section: 15.14
169) What is the Birch reduction product of the following reaction?
Na, NH3(l)
EtOH
II
III
IV
a) I
b) II
c) III
d) IV
e) V
Answer: D
Topic: Non-EAS Reactions
Section: 15.16
91
would be:
a) I
b) II
c) III
d) IV
e) V
Answer: C
Section: 15.16
92
would be:
a) I
b) II
c) III
d) IV
e) V
Answer: D
Section: 15.16
93
would be:
a) I
b) II
c) III
d) IV
e) V
Answer: D
Section: 15.16
94
would be:
a) I
b) II
c) III
d) IV
e) V
Answer: E
Section: 15.15
174) SN1 solvolysis of C6H5CH=CHCH2Cl in water produces:

a) C6H5CH2C(OH)=CH2
b) C6H5CH=CHCH2OH
c) C6H5CHOHCH=CH2
d) A mixture of two of these choices.
e) A mixture of all of these choices.
Answer: D
95

Section: 15.15
175) Which compound is capable of undergoing both SN1 and SN2 reactions in ordinary
nonacidic solvents?
Br
Br
Br
Br
Br
II
III
IV
a) I
b) II
c) III
d) IV
e) V
Answer: D
Section: 15.15
176) Which alkyl halide can undergo both SN1 and SN2 reactions in nonacidic solvents?
a) CH3Br
b) CH3CH2CH2Br
CH2
CHCHCH3
Br
c)
d) C6H5CH2CH2CH2Br
CH3
C6H5CCH2Br
e)
CH3
Answer: C
Section: 15.15
96
Question type: fill-in-the-blank
177) 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.
Answer: electrophile; arenium ion; proton
Topic: EAS Mechanism
Section: 15.2
Question type: Molecular Drawing
178) Draw a mechanism that explains the formation of the following product in this FriedelCrafts alkylation:
AlCl3
+
Cl
Answer:
+
AlCl3
C
H2
Cl
Cl
AlCl3
-H+
Topic: Mechanism, Carbocation Stability

Question type: fill-in-the-blank

97
AlCl4-
179) When two different groups are present on a benzene ring, the ___ generally determines the
outcome of an EAS reaction.
Answer: more powerful activating group
Topic: General EAS Reactivity
Section: 15.14
180) Substituent groups affect both ___ and ___ in electrophilic aromatic substitution reactions.
Answer: reactivity; orientation
Section: 15.10
181) 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.
Answer: activating
Section: 15.10
182) 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.
Answer: deactivating
Section: 15.10
183) With the exception of halogens, activating groups are ___ directors and deactivating groups
are ___ directors.
Answer: ortho/para; meta
98

Section: 15.10
Question type: Essay
184) 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
O
Answer: 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 electronpoor. 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 electron-poor,
bromination of this ring would also lead to minor products.
Ring
Ring
A
A
O
HN
O
Br
major products
HN
O
Ring
B
Br
Ring
B

Section: 15.3, 15.10 and 15.11
185) 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
3
E+
2
or
(-H+)
E
O
Which substitution product forms preferentially and why?

99
Answer: 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
O
H
-H+
E
H
E
E+
O
E
E
-H+
O

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

100
E+
E
N
H
N
H
E
N
H
E
N
H
-H+
E
N
H
H
H
E
E+
N
H
E
E
N
H
-H+
N
H
N
H

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

101
E+
E
S
S
H
-H+
E
H
E
E+
S
E
E
-H+
S

188) 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
4
3
E+
or
2
N
1
or
(-H )
E
Which substitution product(s) forms and why?

that is lower in energy/more stable (possesses three good resonance forms), and hence will form
faster.
102
H
N
E+
H
N
divalent, positively charged nitrogen

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

poor resonance structure

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+)

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.
103
NO2
NO2
NO2+
the existance of this "homobenzylic"resonance form

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

form can be drawn

190) 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
4
N
1
E+
(-H+)
instead of
N
or
N
that is lower in energy/more stable (possesses three good resonance forms), and hence will form
faster.
104
Ea
H
Ea
P.E.
+
N
Reaction Progress
Topic: General EAS Reactivity, Mechanisms, Energy Diagrams

nitrated product instead of the 2 nitrated product in the electrophilic aromatic nitration of
naphthalene.
NO2
1
2
NO2
NO2+
instead of
(-H+)
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.
105

substituted product instead of the 3 product in the electrophilic aromatic substitution of furan.
E
3
E+
2
O
instead of
(-H+)
E
O
substituted product), and hence will form faster
106

substituted product instead of the 3 product in the electrophilic aromatic substitution of pyrrole.
E
3
E+
2
N
H
(-H+)
instead of
E
N
H
N
H
107

substituted product instead of the 3 product in the electrophilic aromatic substitution of
thiophene.
E
3
E+
instead of
2
S
(-H+)
E
S
108

195) 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
2
E+
(-H+)
N
H
or
E
N
H
N
H
1
indole

Answer: 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
N
H
109
-H+
N
H
E+
E
N
H
N
H
E
N
H
N
H
E
N
H
N
H
-H+
E
N
H

196) 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

resonance stabilized through the oxygen, without loss of the benzenoid ring aromaticity. This
H
E+
O
110
-H
E+
E
O
O
H
-H+
O

197) 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

forms without aromaticity
H
E
S
111
-H+
E+
E
S
S
H
-H+
S

substituted product instead of the 2 product in the electrophilic aromatic substitution of benzo[b]
thiophene (shown).
E
3
2
S
E+
E
instead of
(-H+)
S
1
benzo[b]thiophene
112
E
S
H
Ea
H
Ea
P.E.
Reaction Progress

substituted product instead of the 2 product in the electrophilic aromatic substitution of benzo[b]
furane (shown).
E
3
2
O
E+
instead of
(-H )
O
O
1
benzo[b]furan
113
E
O
H
Ea
H
Ea
P.E.
Reaction Progress

substituted product instead of the 2 product in the electrophilic aromatic substitution of indole
(shown).
E
3
2
N
H
E+
instead of
+
(-H )
N
H
N
H
indole
resonance stabilized through the nitrogen, without loss of the benzenoid ring aromaticity. This
114
E
N
H
Ea
H
H
P.E.
Ea
E
N
H
Reaction Progress

201) 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.
Answer: 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 1phenyl-1-pentene gives 1-phenyl-1-pentanol, 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.
115
H 2O
H 3 O+
2o, benzylic:
stabilized by
resonance,formed
2o, but not benzylic:

less stable, not
formed to any
almost exclusively
appreciable degree
OH
H
chief product
OH
not detected
Topic: Mechanism, Carbocation Stability

Section: 15.12
202) 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.
Answer: Reaction with Cl2/FeCl3 results in electrophilic aromatic substitution at the o- and ppositions, 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 freeradical halogenation via the benzyl radical intermediate.
Cl2
FeCl3
Cl
Cl
+
Cl
Cl2
heat
Topic: EAS/non-EAS Reactivity

203) Suggest a reasonable synthetic strategy for the synthesis of 3,5-dinitrobenzyl alcohol from
benzaldehyde.
116
NO2
HNO3 (excess)
H2SO4
O2N
heat
Answer: benzaldehyde
NaBH4
H 2O
NO2
OH
O2N
3,5-dinitrobenzyl alcohol
Topic: Synthetic Strategy

Section: 15.14
204) Suggest a reasonable synthetic strategy for the synthesis of 4-methyl-1-phenyl-1-pentanol

from 4-methylpentanoyl chloride, (CH3)2CHCH2CH2COCl
O
OH
NaBH4
H 2O
Cl
O
AlCl3
Answer: 4-methylpentanoyl chloride
4-methyl-1-phenyl-1-pentanol

Section: 15.7
205) Suggest a reasonable synthetic strategy for the synthesis of 6-methyl-3-phenyl-3-heptanol

from 4-methylpentanoyl chloride, (CH3)2CHCH2CH2COCl
O
OH
i) C2H 5MgBr
ii) NH 4Cl
Cl
AlCl3
Answer: 4-methylpentanoyl chloride
6-methyl-3-phenyl-3-heptanol

Section: 15.14
117
1. Br2, FeBr3
2. Mg, ether
3. ethylene oxide
4. H3O+
5. PBr3
6. Mg, ether
7. O
8. H3O+, heat (-H2O

9. HF
Answer:
O
Br2, FeBr3
OH
MgBr
Br
Mg, ether
H3O+
PBr3
O
Br
MgBr
HF
Mg, ether
H 3O +
(-H2O)

Section: 15.14
207) Propose a reasonable synthesis of the following compound from benzene.
multi-step process
Answer:
118
Br2, FeBr3
OH
MgBr
Br
Mg, ether
H3O+
PBr3
O
Br
MgBr
HF
Mg, ether
H 3O +
(-H2O)

Section: 15.14
208) What product would result from the following series of reactions:
O
1. AlCl3
2. SOCl2
O
+
3. AlCl3
Answer:
O
O
SOCl2
AlCl3
O
+
COOH
AlCl3
COCl
O

Section: 15.14
119

Chapter 15 - Test Bank Chem 200

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Chapter 15 - Test Bank Chem 200

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Package Title: Solomons Test Bank

Course Title: Solomons 11e

Question Type: Multiple Choice

1) Which of these is the rate-determining step in the nitration of benzene?

2) Which of these is the rate-determining step in the sulfonation of benzene?

3) Which of these is the rate-determining step in the bromination of benzene?

Topic: Mechanisms and Intermediates

Topic: Other EAS Considerations

15) Undesired polysubstitution of an aromatic nucleus is most likely to be encountered in the

Topic: Other EAS Considerations

18) Which one of these molecules can be a reactant in a Friedel-Crafts reaction?

19) Which one of these molecules can be a reactant in a Friedel-Crafts reaction?

Topic: Functional Group Tests

26) Which of the following reactions could be used to synthesize tert-butylbenzene?

27) Which of the following reactions could be used to synthesize tert-butylbenzene?

28) Which of the following reactions could be used to synthesize tert-butylbenzene?

29) Consider the following reaction: what is the expected product?

33) Which of the following reactions would produce isopropylbenzene?

34) Which of these is a satisfactory synthesis of 1-chloro-2-phenylethane?

35) Which of these is a satisfactory synthesis of 1-chloro-2-phenylethane?

36) Which of the following reactions would produce cumene?

41) The major product(s) of the following reaction,

a) Substitution occurs in ring B, p- to the methylene group.

Section: 15.7 and 15.8

43) What would be the product of the following reaction sequence?

44) What would be the product of the following reaction sequence?

45) What would be the product of the following reaction sequence?

46) What would be the product of the following reaction sequence?

47) What would be the product of the following reaction sequence?

48) What would be the product of the following reaction sequence?

49) Which would be the product of the following reaction sequence?

50) Which would be the product of the following reaction sequence?

51) Which would be the product of the following reaction sequence?

52) Which would be the product of the following reaction sequence?

53) Which would be the product, X, of the following reaction sequence?

54) Which would be the product, X, of the following reaction sequence?

55) The major product(s), D, of the following reaction,

56) The major product, D, of the following reaction,

Difficulty Level: Medium

65) Which would be the major product(s) of the following reaction?

68) What would be the major product(s) of the following reaction?

Topic: Reaction Products

73) The major product(s), D, of the following reaction

74) Which would be the major product(s) of the following reaction?

e) I and III in roughly equal amounts.

75) Which would be the major product(s) of the following reaction?

76) What would be the major product(s) of the following reaction?

77) What would be the major product(s) of the following reaction?

Topic: Reaction Products

78) The major product(s), C, of the following reaction,

79) The major product(s), A, of the following reaction,

80) The major product(s) of the following reaction,

81) The major product(s) of the following reaction,

82) The major product(s), A, of the following reaction,

83) What would be the major product of the following reaction?

84) What would be the major product of the following reaction?

85) What would be the major product of the following reaction?

88) What would be the major product of the following reaction?

93) The reaction of benzene with

in the presence of anhydrous aluminum

94) The reaction of benzene with

in the presence of anhydrous aluminum

95) The reaction of benzene with

in the presence of anhydrous aluminum chloride