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
1
Answer: C

Section: 15.2
4) Which of the following structures contribute(s) to the resonance hybrid of the intermediate
for m ed when brom obenzene underg oes para-chlorination?
. . .. ..
: Br: : Br+ : Br : .. : Br :
+
+ +
H Cl H Cl H Cl H Cl
I II III IV
a) I
b) II
c) III
d) IV
e) All of these choices.
Answer: E

Section: 15.11
5) Which of the following structures contribute(s) to the resonance hybrid of the

intermediate formed when chlorobenzene undergoes para-chlorination?
.. .. .. ..
:Cl : :Cl + : Cl : :Cl :
+
+ +
H Cl H Cl H Cl H Cl
I II III IV
a) I
b) II
c) III
d) IV
Answer: E

Section: 15.11
6) Which of the following structures contribute(s) to the resonance hybrid of the

intermediate formed when acetanilide undergoes para-bromination?
: NHCOCH3 + :NHCOCH3 : NHCOCH3
NCOCH3
+
+ +
H Br H Br H Br H Br
I 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
I 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
in t erme d iate form ed when nitrobe n zene undergoes meta-chlorination?
.. . . .. . . ..
:O : O: ..
: O : O: : O : O:
N N N
+ +H
H H
Cl
Cl Cl
+
I II 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?
O O O O
HN HN HN HN
Br H Br H H H
Br Br
II III IV
I
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
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
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
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?
H2SO4
a) C6H6 + CH2=C(CH3)2
b) C6H6 + (CH3)3COH c) C6H6 + (CH3)3CCl

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

NH2
Br2, H2O
?
Cl
NH2 Cl
Br Br Br Br Br Br
H2N Cl
Cl NH2
I II III
NH2 NH2
Br Br
Br
Cl Cl
IV V
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
OH
Benzene
b) H2SO4
CH3CHCH3
Cl
Benzene
AlCl3
c)
d)
Benzene
C 3CH2CH2Cl
H
AlCl3
Answer: E
Topic: Synthesis
Section: 15.6
a) CH3CHCH3 OH
Benzene
b) H2SO4
CH3CHCH3
Benzene Cl
c) AlCl3
CH3CH2CH2Cl
Benzene
d) AlCl3
Answer: E
Topic: Synthesis
Section: 15.6
a)
b)
CH3CHCH3
Cl
Benzene
c) AlCl3
Benzene CH3CH2CH2Cl
d) AlCl3
Answer: E
Topic: Synthesis
Section: 15.6
33) Which of the following reactions would produce isopropylbenzene?
Cl
Benzene
a) AlCl3
Benzene
b) HF
OH
Benzene
c) H2SO4
Br
Benzene
AlCl3
d)
Answer: E
Topic: Synthesis
Section: 15.6
34) Which of these is a satisfactory synthesis of 1-chloro-2-phenylethane?

a) C6H5CH2CH3 + Cl2, Fe ⎯⎯
b) C6H5CH2CH3 + Cl2, 400C ⎯⎯
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, 400C ⎯⎯
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) AlCl3
Benzene
b) HF
OH
Benzene
c) H2SO4
Br
Benzene
AlCl3
d)
Answer: E
Topic: Synthesis
Section: 15.6
37) Which of the following reactions would yield cumene as the major product?
CH3CH CH2
Benzene
a) H2SO4
CH3CHCH3
OH
Benzene
b) H2SO4
CH3CHCH3
Cl
Benzene
c) AlCl3
CH3CH2CH2Cl
Benzene
d) AlCl3
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 NH2
I + CH3Cl AlCl3 CH3

and
CH3
NH2 NH2
AlCl3
II + CH3Cl
CH3
III + CH3CH2CH2Cl
A CH2CH2CH3
lC
l3
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 AlCl3
excess ?
HN CH3Cl
O O O
HN HN HN
I II III
O O
HN HN
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: E

O2N
O
AlCl3
+ ?
Cl
O2N O2N O2N O
O O
I II III
O2N O2N
IV V
O O
a) I
b) II
c) III
d) IV
e) V
Answer: A

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

O
O
+ AlCl3
Cl ?
O O
O
O O
O
I II
III
O
O 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?
O2 N
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 these choices. No reaction will occur.
Answer: A

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

OH i) SOCl2
O ii) C6H6, AlCl3 ?
iii) Zn(Hg), HCl, heat
O O OH
OH
I II III
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: E


OH i) SOCl2
O ii) C6H6, AlCl3 ?
iii) H2NNH2/KOH
O O OH
OH
I II III
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: E


OH i) PCl5
?
O ii) C6H6, AlCl3
iii) Zn(Hg), HCl, heat
O O OH
OH
I II III
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: E

a) I
b) II
c) III
d) IV
e) V
Answer: E


OH
i) SOCl2
?
ii) C6H6, AlCl3
O iii) Zn(Hg), HCl, heat
O OH
I II III
OH
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: B


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
I SO2 II CO2 CH2
O III
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: C

a) I
b) II
c) III
d) IV
e) V
Answer: C


O i) PCl5
OH ii) benzene, AlCl3 ?
iii) Zn(Hg), HCl
SO2 CO2 CH2
I II III
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: C

a) I
b) II
c) III
d) IV
e) V
Answer: C

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

O
O
Ph
i) benzene, AlCl3 OH
O
Ph ii) Zn(Hg), HCl X +
SO2 CO2 CH2
I II III
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: C

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

a) I
b) II
c) III
d) IV
e) V
Answer: C

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

O
C CH2 Br2
FeBr3 D
O O
C C
Br CH2 CH2
Br
I II
O O
C C
CH2 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,

O
H2SO4
D
SO3
O O
HO3S
I II
SO3H
SO3H
O O
SO3H
IV
III
SO3H
would be:
a) I
b) II
c) III
d) IV
e) V
Answer: D

COOH
Br2
SO3H FeBr3 ?
COOH SO3H SO3H

COOH
Br Br
COOH Br SO3H
COOH
SO3H
I II III IV
a) I
b) II
c) III
d) IV
e) Equal amounts of II and IV.
Answer: C

NO2
Br2
FeBr3 ?
SO3H
NO2
NO2 NO2 NO2
Br Br
SO3H SO3H Br SO3H SO3H

Br
I II III IV
a) I
b) II
c) III
d) IV
Answer: C

O
Br2, FeBr3
O
?
O O
O
Br
O
O
Br O
I II Br
III
Br
O
O
O Br
O
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: D

1 equiv. Br2 ?
FeBr3
Br
Br
Br
I II
III
Br
Br
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: C

1 equiv. Cl2 ?
FeCl3
Cl
Cl
Cl
I II
III
Cl
Cl
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: C

O
Cl2, FeCl3
?
HN
Cl
O O O
Cl
HN HN
HN
Cl
I II III
O O
Cl
HN HN
Cl
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: E

1 equivalent Br2
?
O FeBr3
Br
O O O Br
Br
I II III
Br
Br
IV V
O
a) I
b) II
c) III
d) IV
e) V
Answer: C

64) What would you expect to be the major product obtained from the monobromination of m-
dichlorobenzene?
Cl
Cl Cl
Br
Cl
Cl Br Cl
Br
I II 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?

H3COO
Br2, FeBr3
?
H3COO H3COO H3COO
Br
Br Br2 Fe
I 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

O
HNO3 ?
HN H SO , heat
2 4
NO2
O O O
O2N
HN HN HN
O2N
I II III
O O
HN HN
NO2
NO2
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: E

O
HNO3
O H2SO4, heat ?
O O
O
O2N
O
NO2
O
O2N O
I II III
NO2
O
O
O
O
NO2
IV V
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 ?
NO2 H2SO4, heat
CO2H
CO2H
NO2 CO2H CO2H
O2 N
NO2 NO2
O2 N NO2 NO2
NO2
I II III IV
a) I
b) II
c) III
d) IV
e) Approximately equal amounts of II and IV.
Answer: C

1 equiv. HNO3
H2SO4, heat ?
O2N
NO2
I II NO2
III
NO2
O2N
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: C

HNO3
HN H2SO4, heat ?
O2N
HN HN
NO2
HN
O2N
I II III
NO2
HN
HN
NO2
IV V
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
m- dichlorobenzene?
Cl Cl
Cl
NO2
Cl Cl
O2N Cl
NO2
I II III
a) I
b) II
c) III
d) Equal amounts of I and II.
e) Equal amounts of I, II and III.
Answer: B
72) What would you expect to be the major product(s) obtained from the following reaction?
HO O
HNO3
?
SO3H
H2SO4 , heat
HO O
HO O HO O HO O
NO2 O2N
SO3H
SO3H NO2 O2N SO3H SO3H
I II III IV
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

O HNO3
D
H2SO4
O
O
O2 N
I NO2 II
NO2
O O
NO2
III IV
would be:
a) I
b) II
c) III
d) IV
e) Equal amounts of I and II.
Answer: D


HO O
HNO3
?
H2SO4
HO HO HO O
O NO2
O
NO2 HO3S
I II III
a) I
b) II
c) III
Answer: A


H3COO
HNO3 ?
H2SO4
H3COO H3COO H3COO
NO2
NO2 HO3S
I II III
a) I
b) II
c) III
Answer: A


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


O
H2SO4
SO3
?
NO 2
O
O O O
SO3H HO3S
NO2
NO2 HO3S NO2 NO2
SO3H
I II III IV
a) I
b) II
c) III
d) Equal amounts of I and IV.
Answer: C
78) The major product(s), C, of the following reaction,
Cl
SO3
H2SO4 C
Cl
Cl
Cl Cl
SO3H
Cl
Cl HO3S Cl
SO3H
I II 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 A
400 - 600 oC
CH3CH2
Cl CH3CH2 ClCH2CH2 CH3CH
Cl Cl
I II III IV
would be:
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
I II III IV
a) I
b) II
d) III
e) IV
Answer: A

Section: 15.12

excess NBS
?
ROOR
Br
Br Br Br
Br
Br
Br
Br
I II III IV
a) I
b) II
d) III
e) IV
Answer: D

Section: 15.12
NBS
?
ROOR
Br
Br
Br
Br
I II III IV
would be:
a) I
b) II
d) III
e) IV
Answer: E

Section: 15.12
83) What would be the major product of the following reaction?
CH2CH2CH3 Cl2
400 oC ?
Cl CH2CH2CH3 CH2CH2CH3 CHCH2CH3
Cl Cl
I II III
CH2CHCH3 CH2CH2CH2Cl
Cl
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: C

Section: 15.12

NBS
?
ROOR
Br
Br
Br Br Br
I II III V
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
I III
II IV
Br Br
IV
a) I
b) II
c) III
d) IV
e) V
Answer: C

Section: 15.12
Cl2
peroxides
?
Cl
Cl
Cl
I II
III
Cl
Cl
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: E

Section: 15.12
Cl2
light
?
Cl
Cl
Cl
I II
III
Cl
Cl
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: E

Section: 15.12

NBS, ROOR ?
light
Br
Br
Br
I II III
Br
Br
IV V
a) I
b) II
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 CCl3
Br
Br
Cl
Br
I II III IV
a) I
b) II
c) III
d) IV
e) A mixture of III and IV.
Answer: B

O
N HNO3
N H2SO4, heat ?
O O NO2 O
O 2N N N N
N N
N
O 2N
I II III
O
O
N
N
N
N
NO2
IV
NO2
a) I
b) II
c) III
d) IV
e) V
Answer: E

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?
I II III
IV V
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 III
I
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: D

94) The reaction of benzene with in the presence of anhydrous aluminum

II III
I
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: D

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

96) The reaction of benzene with

produces principally which of these? in the presence of anhydrous aluminum chloride
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?
CO2H CO2H CO2H
NO2
Br NO2 Br
NO2 Br
I II III
Br
CH3
Br
NO2
NO2 CO2H
IV V
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
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
Cl ii) N-Bromosuccinimide, peroxides
+ ?
iii) CH3ONa, CH3OH, heat
iv) m-CPBA
v) CH3MgBr
vi) NH4Cl
Br
HO
HO
I II III
HO
HO
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: D
Topic: Reaction products

Section: 15.6, 15.12, 15.13
i) HF
ii) N-Bromosuccinimide, peroxides
+ ?
iv) m-CPBA
v) CH3MgBr
vi) NH4Cl
Br
HO
HO
I II III
HO
HO
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: D

Section: 15.6, 15.12, 15.13
i) BF3
OH ii) N-Bromosuccinimide, peroxides
+ ?
iv) m-CPBA
v) CH3MgBr
vi) NH4Cl
Br
HO
HO
I II III
HO
HO
IV V
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) -CN
e) -CO2H
Answer: A
Topic: Directing Effects

Section: 15.10
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) -CN
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.
O
Cl COOH Cl NHCOCH3 CCH3
Cl
NO2
OH CH3 CH2CH3
I II III IV V
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?
HO O
O
HO O
O HO
HO O
OH
I II III IV V
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
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
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
Section: 15.10
114) Arrange the following compounds in order of decreasing reactivity in

electrophilic substitution:
O
O Br NO2
I II III IV V
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
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
transformation? ethylbenzene ⎯⎯ 2- and 4-chloro-1-ethylbenzene

b) Cl2, FeCl3
c) SOCl2
d) C2H5Cl, AlCl3
Answer: B
Topic: Reagents
transformation? t-butylbenzene ⎯⎯⎯ p-chloro substitution product

b) Cl2, FeCl3
c) SOCl2
d) C2H5Cl, AlCl3
e) HCl, peroxide
Answer: B
Topic: Reagents
transformation? 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
+
o-tert-butylbenzenesulfonic acid
a) HNO3/H2SO4
b) tert-C4H9Cl/AlCl3
c) H2SO3/peroxides
d) SO3/H2SO4
e) SO2/H2SO3
Answer: D
Topic: Reagents
transformation? 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
transformation? 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
transformation? cumene ⎯⎯⎯ 2- and 4-chlorocumene

b) Cl2, FeCl3
c) SOCl2
d) C2H5Cl, AlCl3
e) HCl, peroxides
Answer: B
Topic: Reagents
transformation? toluene ⎯⎯⎯ benzyl bromide
a) Br2, FeBr3
b) N-Bromosuccinimide, ROOR, h
c) HBr
d) Br2/CCl4
e) NaBr,
H2SO4 Answer:
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) O
1) CH3CH2CCl , AlCl3 2) Zn(Hg), HCl 3) Br2, Fe
d) O
e) (1) (CH3)2CHCl, AlCl3 (2) Br2,Fe
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
c) O
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 Br CHO NO2
I II III IV V
a) I
b) II
c) III
d) IV
e) V
Answer: A
Topic: Relative Reactivities

Section: 15.11
130) Which of the following compounds would be least reactive toward
OH CH3 Br CHO NO2
I II III IV V
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 CF3 Cl NH2
I II III IV V
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

O
O
NO2 NH
NO2
I II III IV V
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

O
O
NO2 NH NH2
NO2
I II III IV V
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?
O O
O CF3 OH NH
I II III IV V
a) I
b) II
c) III
d) IV
e) V
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?
HO O
OH NH2 OCH3 CH3
I II III IV V
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?
O
HO O O O
O NH2 OCH3
I II III IV V
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 O NH OCH3 CH3
I II III IV V
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
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
CH3 H +CH2 CH2 CH3
H
+
+ +
I II + IV
III IV
a) I
b) II
c) III
d) IV
e) V
Answer: A
Topic: Non-EAS Relative Rates and Intermediates

Section: 15.12
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
c) Br
CH3
C6H5CCH2Br
d) CH3
Br
C6H5CCH3
e) CH3
Answer: A

Section: 15.15
143) Which alkyl halide would be most reactive in an SN1 reaction?
a) C6H5CH2CH2CH2Br
C6H5CH2CHCH3
b) Br
CH3
C6H5CH2CBr
c) CH3
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
b) Cl
c) (C6H5)2CHCl
C6H5CHCl
d) CH3
e) (C6H5)3CCl
Answer: A
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) C6H5CCH
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) C6H5CCH
c) C6H5COCH3
d) C6H5CH2CH2CH3
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) C6H5CCH
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, 400C ⎯⎯
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?

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

b) H3O+, heat
c) Mg; then CO2; then H3O+
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:
CH3CCl (CH3)3CCl
Benzene
a) AlCl3 AlCl3
O
(CH3)3CCl CH3CCl
Benzene
b) AlCl3 AlCl3
O
CH3CCl
(CH3)2C CH2
Benzene
c) AlCl3 HF
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?
HNO3/H2SO4 CH3Cl 1. KMnO4, NaOH, heat

Benzene
a) heat AlCl3 2. H3O+
HNO3/H2SO4 1. KMnO4, NaOH, heat
Toluene
b) heat 2. H3O+
1. KMnO4, NaOH, heat HNO3/H2SO4
Toluene
c) 2. H3O+ heat
d) More than one of these choices.
Answer: C
Topic: Synthesis
Section: 15.14
153) Which of the following would be the best synthesis of 1,4-dimethyl-2-nitrobenzene?
HNO3 2 CH3Cl
Benzene product
a) H2SO4 2 AlCl3
HNO3
Toluene CH3Cl
b) H2SO4 product
HNO3 AlCl3
p-Xylene
c) H2SO4
CH3Cl
m-Nitrotoluene
d) AlCl3
e) All of these choices are equally good.
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.
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
several
Benzene ?
steps Cl
CH3CH2Cl Cl2
C6H6 product
a) AlCl3 FeCl3
Cl2 CH3CH2Cl
C6H6 product
b) FeCl3 AlCl3
O
CH3CCl Cl2 Zn(Hg)

C6H6 product
AlCl3 FeCl3 HCl
c)
O
CH3CCl
Zn(Hg) Cl2
C6H6 AlCl3 product
d) HCl FeCl3
e) None of these syntheses is satisfactory.
Answer: C
Topic: Synthesis
Section: 15.14
CH2CH3
several
Benzene ?
steps Cl
CH3CH2Cl Cl2
C6H6 product
a) AlCl3 FeCl3
Cl2 CH3CH2Cl
C6H6 product
b) FeCl3 AlCl3
O
CH3CCl Cl2 H2NNH2

C6H6 product
AlCl3 FeCl3 KOH
c) O
CH3CCl Zn(Hg) Cl2

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

product
AlCl3 FeCl3 HCl
O
CH3CCl Zn(Hg) Cl2

product
AlCl3 HCl FeCl3
Answer: D
Topic: Synthesis
Section: 15.14
several
steps
Cl
CH3CH2Cl Cl2
C6H6 product
a) AlCl3 FeCl3
Cl2 CH3CH2Cl
C6H6 product
b) FeCl3 AlCl3
O
CH3CCl Cl2 Zn(Hg)

C6H6 product
c) AlCl3 FeCl3 HCl
O
CH3CCl H2NNH2 Cl2

C6H6 product
d) AlCl3 KOH FeCl3
Answer: D
Topic: Synthesis
Section: 15.14
several
steps
Cl
CH3CH2Cl Cl2
C6H6 product
a) AlCl3 FeCl3
Cl2 CH3CH2Cl
C6H6 product
b) FeCl3 AlCl3
O
CH3CCl Cl2 H2NNH2

C6H6 product
c) AlCl3 FeCl3 KOH
O
CH3CCl H2NNH2 Cl2

C6H6 product
d) AlCl3 KOH FeCl3
Answer: D
Topic: Synthesis
Section: 15.14
161) Which is the best sequence of reactions for the preparation of p-bromostyrene from
ethylbenzene?
NBS, h
ethylbenzene Br2 KOH
product
a) CCl4 Fe CH3CH2OH
ethylbenzene Br2
product
b) Fe
ethylbenzene NBS, h
product
c) CCl4
ZnO
ethylbenzene Br2 product
d) 630 oC
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
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
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
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
I II III IV V
a) I
b) II
c) III
d) IV
e) V
Answer: D
Topic: Non-EAS Reactions

Section: 15.16
would be:
a) I
b) II
c) III
d) IV
e) V
Answer: C

Section: 15.16

would be:
a) I
b) II
c) III
d) IV
e) V
Answer: D

Section: 15.16

would be:
a) I
b) II
c) III
d) IV
e) V
Answer: D

Section: 15.16

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
Section: 15.15
175) Which compound is capable of undergoing both SN1 and SN2 reactions in ordinary
nonacidic solvents?
Br Br Br
Br
Br
I II III IV V
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
c) Br
d) C6H5CH2CH2CH2Br
CH3
C6H5CCH2Br
e) CH3
Answer: C

Section: 15.15
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 Friedel-
Crafts alkylation:
AlCl3
+
Cl
Answer:
+ AlCl3 C Cl AlCl3 AlCl4 -

H2
Cl
-H+
Topic: Mechanism, Carbocation Stability

Question type: fill-in-the-blank

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

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 HN
Br2
FeBr3 ?
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 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 electron-poor,
bromination of this ring would also lead to minor products.
Ring Ring
A A
O O
HN Br + HN major products
O O
Ring Br Ring
B 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+
or
2 + E
(-H )
O O O
1
Which substitution product forms preferentially and why?
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 E E
O O O O
H H H
-H+
O E
H H
E
E E
E+ -H+
O O O 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+
or
2 + E
(-H )
N N N
H H H
1
E+
E
E E
N N
H H N N
H
H H H H
-H+
E
H H
E
H
E
-H+
+ E
E
N N N N
H H H 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+
or
2
(-H+) E
S S S
1
E+
E E E
S S S S
H H H
-H+
S E
H
H
E
+ E E
E
-H+
S S S 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
E
3 E+
or or
2 (-H+)
N N E N N
1
Which substitution product(s) forms and why?
that is lower in energy/more stable (possesses three good resonance forms), and hence will form
faster.
H H H
N N N N
E+ E E E
divalent, positively charged nitrogen

poor resonance structure
H H H
E+
E E E
N N N N
H E H E
E+ H E
N N
N N
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.
H NO2 H 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
E
3 E+
instead of or
2 (-H+)
N N N E N
1
that is lower in energy/more stable (possesses three good resonance forms), and hence will form
faster.
H E
‡
‡ +
H +
N
N
E
Ea
H
P.E. Ea E
+
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.
substituted product instead of the 3 product in the electrophilic aromatic substitution of furan.
E
3
E+
instead of
2
(-H+) E
O O O
substituted product), and hence will form faster
substituted product instead of the 3 product in the electrophilic aromatic substitution of pyrrole.
E
3
E+
instead of
2 +
(-H ) E
N N N
H H H
1
substituted product instead of the 3 product in the electrophilic aromatic substitution of
thiophene.
3 E
+
E
2 instead of
(-H+)
S E
S
S
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.
3 E
E+
2 E or
N (-H+)
N
H N
H
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 H
E
E E -H+
E+
N N N N
H H H H
E+
E E
N N N
H H H H
H
E E E
N N N
H H H H
H H
-H+
N E
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.
3 E
E+
2 E or
(-H+)
O O O
1
benzo[b]furan
resonance stabilized through the oxygen, without loss of the benzenoid ring aromaticity. This
H H
E
E E -H+
E+
O O O O
E+
E E
O O O
H H
E E E
O O O
H H H
-H+
O E

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+ E or
2
S (-H )+
S S
1
benzo[b]thiophene
forms without aromaticity
H H
E
E E -H+
E+
S S S S
E+
E E
S S S
H H
E E E
S S S
H H H
-H+
S E

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

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

substituted product instead of the 2 product in the electrophilic aromatic substitution of indole
(shown).
3 E
E+
2 instead of E
N (-H+) N
H N H
1 H
indole
resonance stabilized through the nitrogen, without loss of the benzenoid ring aromaticity. This
‡
‡
E
NH
Ea H
H
P.E. Ea
E
NH
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 1-
phenyl-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.
H3O+ +
H2O
H OH
o
2 , benzylic:
stabilized by H
resonance,formed chief product
almost exclusively
t zylic: lessHstable,
not formed to any
+ +
n appreciable degree
2 o
o
t
,
H
b
+
b e OH
u n 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 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 Cl +
FeCl3 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.
HNO (excess)
NO2 NaBH NO2
3 4
O H 2O OH
O H2SO4 O2 N O2 N
heat
Answer: benzaldehyde 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
Cl NaBH4
O AlCl3 H2O
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
O
i) C2H5MgBr
Cl
AlCl3 ii) NH4Cl
Answer: 4-methylpentanoyl chloride 6-methyl-3-phenyl-3-heptanol

Section: 15.14
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
MgBr H O+ OH
Br 3
Br2, FeBr3 Mg, ether
PBr3
Br
MgBr
HF
Mg, ether +
H3O
(-H2O)

Section: 15.14
207) Propose a reasonable synthesis of the following compound from benzene.
multi-step process
OH
Answer:
Br MgBr
O
H3O+ PBr3
Br2, FeBr3 Mg, ether
Br
MgBr
HF
Mg, ether +
H3O
(-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
AlCl3 SOCl2
O +
O COOH O
O
AlCl3
COCl
O

Section: 15.14

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?

a) Protonation of nitric acid by sulfuric acid

Topic: Mechanisms and Intermediates

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

a) Formation of SO3 from sulfuric acid

Topic: Mechanisms and Intermediates

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

a) Complexation of bromine with the iron(III) bromide catalyst

Topic: Mechanisms and Intermediates

Topic: Mechanisms and Intermediates

5) Which of the following structures contribute(s) to the resonance hybrid of the

Topic: Mechanisms and Intermediates

6) Which of the following structures contribute(s) to the resonance hybrid of the

Topic: Mechanisms and Intermediates

Topic: Mechanisms and Intermediates

Topic: Mechanisms and Intermediates

Topic: Mechanisms and Intermediates

Topic: Mechanisms and Intermediates

Topic: Other EAS Considerations

Topic: Other EAS Considerations

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

Topic: Other EAS Considerations

Topic: Other EAS Considerations

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

Topic: Other EAS Considerations

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

Topic: Other EAS Considerations

Topic: Nomenclature, Functional Group Tests

Topic: Nomenclature, Reaction Products

Topic: Nomenclature, Reaction Products

Topic: Nomenclature, Reaction Products

Topic: Nomenclature, Reaction Products

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

b) C6H6 + (CH3)3COH c) C6H6 + (CH3)3CCl

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?

a) C6H5CH2CH3 + Cl2, Fe ⎯⎯

36) Which of the following reactions would produce cumene?

NH2 NH2 NH2

I + CH3Cl AlCl3 CH3

Topic: Reaction Products

Topic: Reaction Products

O2N O2N O2N O

Topic: Reaction Products

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

Topic: Reaction Products

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

Topic: Reaction Products

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

Topic: Reaction Products

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

Topic: Reaction Products

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

Topic: Reaction Products

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

Topic: Reaction Products

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