Professional Documents
Culture Documents
Answer: C
Topic: Mechanisms and Intermediates
Section: 15.2
Difficulty Level: Medium
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
Topic: Mechanisms and Intermediates
Section: 15.11
Difficulty Level: Medium
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
II
III
IV
a) I
b) II
c) III
d) IV
e) All of these choices.
Answer: E
Topic: Mechanisms and Intermediates
2
Section: 15.11
Difficulty Level: Medium
6) Which of the following structures contribute(s) to the resonance hybrid of the intermediate
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
e) All of these choices.
Answer: E
Topic: Mechanisms and Intermediates
Section: 15.11
Difficulty Level: Medium
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
e) None of these choices.
Answer: B
Topic: Mechanisms and Intermediates
Section: 15.11
Difficulty Level: Medium
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
Topic: Mechanisms and Intermediates
Section: 15.11
Difficulty Level: Medium
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
Topic: Mechanisms and Intermediates
Section: 15.11
Difficulty Level: Medium
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
Topic: Mechanisms and Intermediates
Section: 15.11
Difficulty Level: Medium
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
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
Topic: Other EAS Considerations
Section: 15.2
Difficulty Level: Medium
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
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
Topic: Other EAS Considerations
Section: 15.10 and 15.11
Difficulty Level: Medium
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
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
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
Difficulty Level: Medium
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
Section: 14.2 and 15.6
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
Topic: Nomenclature, Reaction Products
Section: 14.2 and 15.6
Difficulty Level: Hard
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
Topic: Nomenclature, Reaction Products
Section: 14.2, 15.3, and 15.8
Difficulty Level: Hard
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
c) 1-bromo-3-chlorobenzene
d) 4-bromoanisole
e) 3-bromoanisole
Answer: D
Topic: Nomenclature, Reaction Products
Section: 14.2, 15.3, and 15.8
Difficulty Level: Hard
H2SO4
10
b) C6H6 + (CH3)3COH
c) C6H6 + (CH3)3CCl
d) All of these choices.
e) None of these choices.
H2SO4
AlCl3
Answer: D
Topic: Synthesis
Section: 15.6
Difficulty Level: Easy
H2SO4
b)
c) C6H6 + (CH3)3CCl
d) All of these choices.
e) None of these choices.
AlCl3
Answer: D
Topic: Synthesis
Section: 15.6
Difficulty Level: Easy
a)
b)
c) C6H6 + (CH3)3CCl
d) All of these choices.
e) None of these choices.
AlCl3
Answer: D
Topic: Synthesis
11
Section: 15.6
Difficulty Level: Easy
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
Difficulty Level: Easy
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)
e) All of these choices.
Answer: E
Topic: Synthesis
Section: 15.6
Difficulty Level: Medium
31) Which of the following reactions would yield isopropylbenzene as the major product?
a)
CH3CHCH3
Benzene
b)
OH
H2SO4
CH3CHCH3
Benzene
c)
Cl
AlCl3
CH3CH2CH2Cl
Benzene
AlCl3
d)
e) All of these choices.
Answer: E
Topic: Synthesis
Section: 15.6
Difficulty Level: Medium
32) Which of the following reactions would yield isopropylbenzene as the major product?
a)
13
b)
CH3CHCH3
Benzene
c)
Benzene
Cl
AlCl3
CH3CH2CH2Cl
AlCl3
d)
e) All of these choices.
Answer: E
Topic: Synthesis
Section: 15.6
Difficulty Level: Medium
Benzene
a)
Benzene
b)
AlCl3
HF
OH
Benzene
H2SO4
c)
Br
Benzene
AlCl3
d)
e) All of these choices.
Answer: E
Topic: Synthesis
Section: 15.6
Difficulty Level: Medium
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
Difficulty Level: Medium
Benzene
a)
Benzene
b)
AlCl3
HF
OH
Benzene
H2SO4
c)
Br
Benzene
AlCl3
d)
e) All of these choices.
Answer: E
15
Topic: Synthesis
Section: 15.6
Difficulty Level: Hard
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)
e) All of these choices.
Answer: E
Topic: Synthesis
Section: 15.6
Difficulty Level: Hard
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
d) All of these choices.
e) None of these choices.
Answer: E
Topic: Reaction Products
Section: 15.6 and 15.8
Difficulty Level: Easy
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
Topic: Reaction Products
Section: 15.6 and 15.8
Difficulty Level: Medium
40) What would you expect to be the major product obtained from the following reaction?
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
Topic: Reaction Products
Section: 15.7 and 15.8
Difficulty Level: Medium
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
Topic: Reaction Products
Section: 15.7 and 15.8
Difficulty Level: Medium
42) What might be predicted to happen when the following substance undergoes Friedel-Crafts
acylation?
O2N
CH2
19
OH
OH
II
IV
III
a) I
b) II
c) III
d) IV
e) V
Answer: E
Topic: Reaction Products
Section: 15.7 and 15.9
Difficulty Level: Medium
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
Topic: Reaction Products
Section: 15.7 and 15.9
Difficulty Level: Medium
i) PCl5
ii) C6H6, AlCl3
iii) Zn(Hg), HCl, heat
OH
O
OH
II
IV
III
a) I
21
b) II
c) III
d) IV
e) V
Answer: E
Topic: Reaction Products
Section: 15.7 and 15.9
Difficulty Level: Medium
a) I
b) II
c) III
d) IV
e) V
Answer: E
Topic: Reaction Products
Section: 15.7 and 15.9
Difficulty Level: Medium
22
OH
i) SOCl2
ii) C6H6, AlCl3
iii) Zn(Hg), HCl, heat
OH
II
III
O
OH
IV
a) I
b) II
c) III
d) IV
e) V
Answer: B
Topic: Reaction Products
Section: 15.7 and 15.9
Difficulty Level: Medium
23
a) I
b) II
c) III
d) IV
e) V
Answer: B
Topic: Reaction Products
Section: 15.7 and 15.9
Difficulty Level: Medium
SO2
CO2
CH2
II
III
IV
24
a) I
b) II
c) III
d) IV
e) V
Answer: C
Topic: Reaction Products
Section: 15.7 and 15.9
Difficulty Level: Medium
a) I
b) II
c) III
d) IV
e) V
Answer: C
Topic: Reaction Products
Section: 15.7 and 15.9
Difficulty Level: Medium
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
Topic: Reaction Products
Section: 15.7 and 15.9
Difficulty Level: Medium
a) I
b) II
c) III
d) IV
26
e) V
Answer: C
Topic: Reaction Products
Section: 15.7 and 15.9
Difficulty Level: Medium
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
Topic: Reaction Products
Section: 15.7 and 15.9
Difficulty Level: Medium
27
a) I
b) II
c) III
d) IV
e) V
Answer: C
Topic: Reaction Products
Section: 15.7 and 15.9
Difficulty Level: Medium
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
Topic: Reaction Products
Section: 15.3 and 15.10
Difficulty Level: Medium
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
Topic: Reaction Products
Section: 15.3 and 15.10
Difficulty Level: Medium
57) What would you expect to be the major product obtained from the following reaction?
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
Topic: Reaction Products
Section: 15.3 and 15.10
Difficulty Level: Medium
58) What would you expect to be the major product obtained from the following reaction?
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
e) Equal amounts of II and IV.
Answer: C
Topic: Reaction Products
Section: 15.3 and 15.10
31
59) What would you expect to be the major product obtained from the following reaction?
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
Topic: Reaction Products
Section: 15.3 and 15.10
Difficulty Level: Medium
60) What would you expect to be the major product obtained from the following reaction?
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
Topic: Reaction Products
Section: 15.3 and 15.10
Difficulty Level: Medium
61) What would you expect to be the major product obtained from the following reaction?
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
Topic: Reaction Products
Section: 15.3 and 15.10
Difficulty Level: Medium
62) What would you expect to be the major product obtained from the following reaction?
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
Topic: Reaction Products
Section: 15.3 and 15.10
Difficulty Level: Medium
63) What would you expect to be the major product obtained from the following reaction?
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
Topic: Reaction Products
Section: 15.3 and 15.10
Difficulty Level: Medium
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
Topic: Reaction Products
Section: 15.3 and 15.10
Difficulty Level: Medium
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
Topic: Reaction Products
Section: 15.3 and 15.10
Difficulty Level: Medium
36
66) What would you expect to be the major product obtained from the following reaction?
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
Topic: Reaction Products
Section: 15.4 and 15.10
Difficulty Level: Medium
67) What would you expect to be the major product obtained from the following reaction?
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
Topic: Reaction Products
Section: 15.4 and 15.10
Difficulty Level: Medium
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
Topic: Reaction Products
Section: 15.4 and 15.10
Difficulty Level: Medium
69) What would you expect to be the major product obtained from the following reaction?
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
Topic: Reaction Products
Section: 15.4 and 15.10
Difficulty Level: Medium
70) What would you expect to be the major product obtained from the following reaction?
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
Topic: Reaction Products
Section: 15.4 and 15.10
Difficulty Level: Medium
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
Topic: Reaction Products
Section: 15.4 and 15.10
Difficulty Level: Medium
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
Topic: Reaction Products
Section: 15.4 and 15.10
Difficulty Level: Medium
HNO3
H2SO4
HO
HO
HO
NO2
NO2
HO3S
II
III
a) I
b) II
c) III
d) I and II in roughly equal amounts.
42
HNO3
H2SO4
H3CO
H3CO
H3CO
NO2
NO2
HO3S
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
Topic: Reaction Products
Section: 15.4 and 15.10
Difficulty Level: Medium
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.
e) Equal amounts of II and IV.
Answer: C
Topic: Reaction Products
Section: 15.5 and 15.10
Difficulty Level: Medium
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.
e) Equal amounts of II and IV.
Answer: C
44
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
Topic: Reaction Products
Section: 15.5 and 15.10
Difficulty Level: Medium
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
Topic: Reaction Products
Section: 15.12
Difficulty Level: Medium
400o - 600oC
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
II
IV
III
a) I
b) II
c) A mixture of I and II.
d) III
e) IV
Answer: A
Topic: Reaction Products
Section: 15.12
Difficulty Level: Medium
46
excess NBS
?
ROOR
Br
Br
Br
Br
Br
Br
Br
Br
II
IV
III
a) I
b) II
c) A mixture of I and II.
d) III
e) IV
Answer: D
Topic: Reaction Products
Section: 15.12
Difficulty Level: Medium
Br
Br
Br
Br
II
III
would be:
a) I
b) II
c) A mixture of I and II.
47
IV
d) III
e) IV
Answer: E
Topic: Reaction Products
Section: 15.12
Difficulty Level: Medium
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
Topic: Reaction Products
Section: 15.12
Difficulty Level: Medium
48
NBS
?
ROOR
Br
Br
Br
Br
Br
III
II
IV
a) I
b) II
c) III
d) IV
e) V
Answer: D
Topic: Reaction Products
Section: 15.12
Difficulty Level: Medium
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
Topic: Reaction Products
Section: 15.12
Difficulty Level: Medium
86) What would you expect to be the major product obtained from the following reaction?
Cl2
peroxides
Cl
Cl
II
Cl
III
Cl
Cl
IV
a) I
b) II
c) III
d) IV
e) V
Answer: E
Topic: Reaction Products
Section: 15.12
Difficulty Level: Medium
87) What would you expect to be the major product obtained from the following reaction?
50
Cl2
light
Cl
Cl
Cl
II
III
Cl
Cl
IV
a) I
b) II
c) III
d) IV
e) V
Answer: E
Topic: Reaction Products
Section: 15.12
Difficulty Level: Medium
II
III
Br
Br
IV
a) I
b) II
51
c) III
d) IV
e) V
Answer: C
Topic: Reaction Products
Section: 15.12
Difficulty Level: Medium
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
Topic: Reaction Products
Section: 15.3 and 15.12
Difficulty Level: Medium
90) What would you expect to be the major product obtained from the following reaction?
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
Topic: Reaction Products
Section: 15.4 and 15.10
Difficulty Level: Hard
91) What would you expect to be the major product obtained from the following reaction?
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
Topic: Reaction Products
Section: 15.4 and 15.10
Difficulty Level: Hard
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
Topic: Reaction Products
Section: 15.6 and 15.8
Difficulty Level: Hard
Cl
II
IV
III
a) I
b) II
c) III
55
d) IV
e) V
Answer: D
Topic: Reaction Products
Section: 15.6 and 15.8
Difficulty Level: Hard
II
IV
III
a) I
b) II
c) III
d) IV
e) V
Answer: D
Topic: Reaction Products
Section: 15.6 and 15.8
Difficulty Level: Hard
56
Cl
II
IV
III
a) I
b) II
c) III
d) IV
e) V
Answer: A
Topic: Reaction Products
Section: 15.6 and 15.8
Difficulty Level: Hard
57
a) I
b) II
c) III
d) IV
e) V
Answer: A
Topic: Reaction Products
Section: 15.6 and 15.8
Difficulty Level: Hard
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
Topic: Reaction Products
Section: 15.3, 15.4, 15.10, and 15.13
Difficulty Level: Hard
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
Topic: Reaction Products
Section: 15.3, 15.4, 15.10, and 15.13
Difficulty Level: Hard
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
Difficulty Level: Hard
100) What product would result from the following series of reactions,
60
i) HF
ii) N-Bromosuccinimide, peroxides
iii) CH3ONa, CH3OH, heat
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
Topic: Reaction Products
Section: 15.6, 15.12, 15.13
Difficulty Level: Hard
101) What product would result from the following series of reactions,
61
i) BF3
ii) N-Bromosuccinimide, peroxides
iii) CH3ONa, CH3OH, heat
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
Topic: Reaction Products
Section: 15.6, 15.12, 15.13
Difficulty Level: Hard
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
Difficulty Level: Easy
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
Topic: Directing Effects
Section: 15.10
Difficulty Level: Easy
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
Topic: Directing Effects
Section: 15.14
Difficulty Level: Easy
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
Topic: Directing Effects
Section: 15.10
Difficulty Level: Easy
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
Topic: Directing Effects
Section: 15.10
Difficulty Level: Easy
107) Which of the following is not an ortho-para director in electrophilic aromatic substitution?
a) -CCl3
b) -OCH3
c) -CH3
d) -F
e) -NH2
Answer: A
64
108) Which of the following is not an ortho-para director in electrophilic aromatic substitution?
a) -SO3H
b) -OCH3
c) -CH3
d) -F
e) -NH2
Answer: A
Topic: Directing Effects
Section: 15.10
Difficulty Level: Easy
109) Which of the following is not an ortho-para director in electrophilic aromatic substitution?
a)
b) -OCH3
c) -CH3
d) -F
e) -NH2
Answer: A
Topic: Directing Effects
Section: 15.10
Difficulty Level: Easy
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
113) Which of these compounds gives essentially a single product on electrophilic substitution of
a third group?
a) p-chlorotoluene
b) m-ethylanisole
c) 1-bromo-2-chlorobenzene
d) m-xylene
e) 3-hydroxybenzoic acid
Answer: D
66
Br
II
III
NO2
IV
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
Topic: Directing Effects
Section: 15.10 and 15.15
Difficulty Level: Medium
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
Section: 15.3 and 15.10
Difficulty Level: Medium
118) Which reagent(s) would you use to carry out the following transformation?
ethylbenzene 2- and 4-chloro-1-ethylbenzene
a) Cl2, light, and heat
b) Cl2, FeCl3
c) SOCl2
d) C2H5Cl, AlCl3
e) None of these choices.
Answer: B
Topic: Reagents
Section: 15.3 and 15.10
Difficulty Level: Medium
119) Which reagent(s) would you use to carry out the following transformation?
t-butylbenzene p-chloro substitution product
a) Cl2, light, and heat
68
b) Cl2, FeCl3
c) SOCl2
d) C2H5Cl, AlCl3
e) HCl, peroxide
Answer: B
Topic: Reagents
Section: 15.3 and 15.10
Difficulty Level: Medium
120) Which reagent(s) would you use to carry out the following 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
Difficulty Level: Medium
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
Section: 15.3 and 15.10
Difficulty Level: Medium
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
Section: 15.5 and 15.10
Difficulty Level: Medium
123) Which reagent(s) would you use to carry out the following 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
Difficulty Level: Medium
124) Which reagent(s) would you use to carry out the following transformation?
ethylbenzene benzoic acid
a) Cl2, light, and heat
b) Cl2, FeCl3
c) KMnO4, OH-, heat (then H3O+)
d) HNO3/H2SO4
e) SO3/H2SO4
Answer: C
Topic: Reagents
Section: 15.13
Difficulty Level: Medium
70
125) Which reagent(s) would you use to carry out the following transformation?
cumene 2- and 4-chlorocumene
a) Cl2, light, and heat
b) Cl2, FeCl3
c) SOCl2
d) C2H5Cl, AlCl3
e) HCl, peroxides
Answer: B
Topic: Reagents
Section: 15.3 and 15.10
Difficulty Level: Hard
126) Which reagent(s) would you use to carry out the following transformation?
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
Difficulty Level: Hard
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
Difficulty Level: Hard
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
Difficulty Level: Hard
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
Difficulty Level: Easy
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
Topic: Relative Reactivities
Section: 15.11
Difficulty Level: Easy
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
Topic: Relative Reactivities
Section: 15.11
Difficulty Level: Easy
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
Topic: Relative Reactivities
Section: 15.11
Difficulty Level: Easy
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
Topic: Relative Reactivities
Section: 15.11
Difficulty Level: Easy
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
Topic: Relative Reactivities
Section: 15.11
Difficulty Level: Easy
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
Topic: Relative Reactivities
Section: 15.11
Difficulty Level: Easy
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
Topic: Relative Reactivities
Section: 15.11
Difficulty Level: Easy
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
Topic: Relative Reactivities
Section: 15.11
Difficulty Level: Easy
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
Topic: Relative Reactivities
Section: 15.11
Difficulty Level: Medium
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
Topic: Relative Reactivities
Section: 15.11
Difficulty Level: Medium
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
a) C6H5CH2CH2CHCH2
CH2
b) C6H5CH2CH2CHCH3
CH3
C6H5CH2CH2CCH3
c)
CH3
d) C6H5CH2CHCHCH3
CH3
e) C6H5CHCH2CHCH3
Answer: E
Topic: Non-EAS Relative Rates and Intermediates
Section: 15.12
Difficulty Level: Medium
b)
CH3
C6H5CH2CHCH3
Br
c)
CH3
C6H5CCH2Br
d)
CH3
Br
C6H5CCH3
e)
CH3
78
Answer: A
Topic: Non-EAS Relative Rates and Intermediates
Section: 15.15
Difficulty Level: Medium
b)
C6H5CH2CBr
CH3
c)
Br
C6H5CCH3
d)
CH3
CH3
C6H5CCH2Br
e)
CH3
Answer: D
Topic: Non-EAS Relative Rates and Intermediates
Section: 15.15
Difficulty Level: Medium
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
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.
e) All of these choices.
Answer: E
Topic: Non-EAS Relative Rates and Intermediates
Section: 15.16
Difficulty Level: Hard
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
Difficulty Level: Easy
147) Benzoic acid can be prepared by the oxidation of which of the following compounds:
a) C6H5CH=CH2
b) C6H5CCH
c) C6H5COCH3
d) C6H5CH2CH2CH3
e) All of these choices.
80
Answer: E
Topic: Synthesis
Section: 15.13
Difficulty Level: Easy
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
e) All of these choices.
Answer: E
Topic: Synthesis
Section: 15.13
Difficulty Level: Easy
CO2H
Br
Br
CO2H
Br
CO2H
d) H2O2, heat
e) KMnO4, OH-, heat; then H3O+
Answer: E
Topic: Synthesis
Section: 15.13
Difficulty Level: Medium
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.
e) None of these choices.
Answer: B
Topic: Synthesis
Section: 15.14
Difficulty Level: Medium
a)
HNO3/H2SO4
CH3Cl
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.
e) None of these choices.
heat
Answer: C
Topic: Synthesis
Section: 15.14
Difficulty Level: Medium
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
Difficulty Level: Hard
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/
OH/heat, followed by H3O+.
c) CH3Cl/AlCl3; then KMnO4/-OH/heat, followed by H3O+; then HNO3/H2SO4.
83
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/
OH/heat, followed by H3O+.
b) CH3Cl/AlCl3; then HNO3/H2SO4; then separation of isomers; then KMnO4/
OH/heat, followed by H3O+.
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
Difficulty Level: Hard
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
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)
e) None of these syntheses is satisfactory.
Answer: C
Topic: Synthesis
Section: 15.14
Difficulty Level: Hard
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)
e) None of these syntheses is satisfactory.
product
Answer: D
Topic: Synthesis
Section: 15.14
Difficulty Level: Hard
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)
e) None of these syntheses is satisfactory.
86
Answer: D
Topic: Synthesis
Section: 15.14
Difficulty Level: Hard
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)
e) None of these syntheses is satisfactory.
Answer: D
Topic: Synthesis
Section: 15.14
Difficulty Level: Hard
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)
e) None of these syntheses is satisfactory.
product
product
Fe
Answer: B
Topic: Synthesis
Section: 15.14
Difficulty Level: Hard
162) Which is the best sequence of reactions for the following transformation?
O
NO2
163) Which is the best sequence of reactions for the following transformation?
O
OH
NO2
164) Which is the best sequence of reactions for the following transformation?
O
OH
NO2
165) Which is the best sequence of reactions for the following transformation?
O
NO2
166) Which is the best sequence of reactions for the following transformation?
OH
O
OCH3
NO2
167) Which is the best sequence of reactions for the following transformation?
O
OCH3
NO2
NO2
Section: 15.14
Difficulty Level: Hard
168) Which is the best sequence of reactions for the following transformation?
O
OH
NO2
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
Difficulty Level: Medium
91
would be:
a) I
b) II
c) III
d) IV
e) V
Answer: C
Topic: Non-EAS Reactions
Section: 15.16
Difficulty Level: Medium
92
would be:
a) I
b) II
c) III
d) IV
e) V
Answer: D
Topic: Non-EAS Reactions
Section: 15.16
Difficulty Level: Medium
93
would be:
a) I
b) II
c) III
d) IV
e) V
Answer: D
Topic: Non-EAS Reactions
Section: 15.16
Difficulty Level: Medium
94
would be:
a) I
b) II
c) III
d) IV
e) V
Answer: E
Topic: Non-EAS Reactions
Section: 15.15
Difficulty Level: Medium
95
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
Topic: Non-EAS Reactions
Section: 15.15
Difficulty Level: Medium
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
Topic: Non-EAS Reactions
Section: 15.15
Difficulty Level: Medium
96
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
Difficulty Level: Easy
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+
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
Difficulty Level: Easy
180) Substituent groups affect both ___ and ___ in electrophilic aromatic substitution reactions.
Answer: reactivity; orientation
Topic: General EAS Reactivity
Section: 15.10
Difficulty Level: Easy
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
Topic: General EAS Reactivity
Section: 15.10
Difficulty Level: Easy
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
Topic: General EAS Reactivity
Section: 15.10
Difficulty Level: Easy
183) With the exception of halogens, activating groups are ___ directors and deactivating groups
are ___ directors.
Answer: ortho/para; meta
98
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
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
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
186) Based on your knowledge of electrophilic aromatic substitution, predict the preferential
position of attack of an electrophile on pyrrole, i.e., does the electrophile E+ attack carbon 2, or
3? Explain your answer.
E
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
187) Based on your knowledge of electrophilic aromatic substitution, predict the preferential
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
102
H
N
E+
H
N
E+
E+
189) Based on your knowledge of electrophilic aromatic substitution, predict the preferential
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+)
103
NO2
NO2
NO2+
(-H+)
H
NO2
NO2+
NO2
(-H+)
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
Answer: The 3 substitution product is favored since it comes from the arenium ion intermediate
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
191) Using a potential energy diagram, explain/illustrate the preferential formation of the 1
nitrated product instead of the 2 nitrated product in the electrophilic aromatic nitration of
naphthalene.
NO2
1
2
NO2
NO2+
instead of
(-H+)
Answer: The 1 substitution product is favored since it comes from the arenium ion intermediate
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
192) Using a potential energy diagram, explain/illustrate the preferential formation of the 2
substituted product instead of the 3 product in the electrophilic aromatic substitution of furan.
E
3
E+
2
O
instead of
(-H+)
E
O
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
106
193) Using a potential energy diagram, explain/illustrate the preferential formation of the 2
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
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.
107
194) Using a potential energy diagram, explain/illustrate the preferential formation of the 2
substituted product instead of the 3 product in the electrophilic aromatic substitution of
thiophene.
E
3
E+
instead of
2
S
(-H+)
E
S
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.
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
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
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
E
S
111
-H+
E+
E
S
S
H
-H+
S
198) Using a potential energy diagram, explain/illustrate the preferential formation of the 3
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
Answer: 3-substitution is preferred, since this leads to a carbocation intermediate that can be
resonance stabilized through the oxygen, 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.
112
E
S
H
Ea
H
Ea
P.E.
Reaction Progress
199) Using a potential energy diagram, explain/illustrate the preferential formation of the 3
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
Answer: 3-substitution is preferred, since this leads to a carbocation intermediate that can be
resonance stabilized through the oxygen, 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.
113
E
O
H
Ea
H
Ea
P.E.
Reaction Progress
200) Using a potential energy diagram, explain/illustrate the preferential formation of the 3
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
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.
114
E
N
H
Ea
H
H
P.E.
Ea
E
N
H
Reaction Progress
115
H 2O
H 3 O+
2o, benzylic:
stabilized by
resonance,formed
almost exclusively
appreciable degree
OH
H
chief product
OH
not detected
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
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
OH
NaBH4
H 2O
Cl
O
AlCl3
4-methyl-1-phenyl-1-pentanol
OH
i) C2H 5MgBr
ii) NH 4Cl
Cl
AlCl3
6-methyl-3-phenyl-3-heptanol
206) What product would result from the following series of reactions,
117
1. Br2, FeBr3
2. Mg, ether
3. ethylene oxide
4. H3O+
5. PBr3
6. Mg, ether
7. O
Answer:
O
Br2, FeBr3
OH
MgBr
Br
Mg, ether
H3O+
PBr3
O
Br
MgBr
HF
Mg, ether
H 3O +
(-H2O)
multi-step process
Answer:
118
Br2, FeBr3
OH
MgBr
Br
Mg, ether
H3O+
PBr3
O
Br
MgBr
HF
Mg, ether
H 3O +
(-H2O)
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
119