ch13 Problems

Chapter Thirteen
Topic: Stability (Alkenes, Cations, Radicals) Section: 13.2

1. Which free radical would be most stable?
A)
B)
C)
D)
E)
Ans: B
2. Which free radical would be least stable?
A)
B)
C)
D)
E)
Ans: D

C H 3
A)
C H 3C C
C H
CH
B)
C H
C C H 2C H
C H
C)
E)
C H 3C C H 2C H
C H
D)
C H 2C H C
C H 3
C H 3C H C H C H
C H
Ans: A
A)
B)
C)
D)
E)
I
II
III
IV
V
Ans: C
II
III
IV

5. Which free radical would be least stable?
A)
B)
C)
D)
E)
II
IV
III
I
II
III
IV
V
Ans: E

V
6.
C H
C H
A)
B)
C)
D)
E)
C H
C H
II
III
Which hydrogen atom(s) of I
susceptible to abstraction by free radicals?
I
II
III
IV
V
Ans: D
C H
IV
C H
C H
C H
is/are most
7.
I
II
V
A)
B)
C)
D)
E)
Which hydrogen atom(s) of

by free radicals?
I
II
III
IV
V
Ans: B
III
IV
is/are most susceptible to abstraction

I
8.
II
V
A)
B)
C)
D)
E)
Which hydrogen atom(s) of

abstraction by free radicals?
I
II
III
IV
V
Ans: C
IV
III
is/are least susceptible to
Topic: Allylic Halogenation Section: 13.2

9.
A)
B)
C)
D)
E)
Which set of conditions does not result in allylic halogenation of an alkene?

Cl2 at 400C
Cl2 in CCl4 at 25C
Cl2, ROOR,h
Br2 at low concentration in CCl4
N-Bromosuccinimide in CCl4, ROOR
Ans: B
Topic: Allylic Halogenation Section: 13.2
CH
10.
C H
A)
B)
C)
D)
E)
CH
CH
CH
C H
IV
III
II
I
Which carbon of V
is predicted to be the major site of
substitution when this alkene reacts with chlorine at 400C?
I
II
III
IV
V
Ans: C
Topic: Multistep Reactions Section: 13.2

11. Which would be the best synthesis?
C H
A)
B)
C)
D)
E)
P ro p e n e
P ro p e n e
P ro p e n e
P ro p e n e
P ro p e n e
Ans: B
C H C H
?
3
Br
C l2 , h
B r2 , C C l4
C l2 , 4 0 0 o C
H C l
N B S , C C l4
C l2 , C C l4
C H 2C H C H 2C l
Br
B r2 , C C l4
B r2, h
C l2 , C C l4
N B S , C C l4
Topic: Allylic Halogenation Section: 13.2 and chapter 10
12. Which of the following compounds is not formed as a result of a chain-termination step
in the free radical chlorination of propene?
A) CH2=CHCH2Cl
B) Cl2
C) CH2=CHCH2CH2CH=CH2
D) HCl
E) All can be formed in chain-termination steps.
Ans: D
Topic: Molecular Orbitals Section: 13.3
13.
A)
B)
C)
D)
E)
The allyl radical has how many bonding molecular orbitals?

1
2
3
4
5
Ans: A

14.
A)
B)
C)
D)
E)
The allyl radical has how many electrons in bonding molecular orbitals?
1
2
3
4
5
Ans: B

15.
A)
B)
C)
D)
E)
The allyl radical has how many electrons in non-bonding molecular orbitals?
1
2
3
4
5
Ans: A
16.
A)
B)
C)
D)
E)
The allyl radical has how many molecular orbitals?

1
2
3
4
5
Ans: C

17.
A)
B)
C)
D)
E)
The HOMO of the allylic radical has how many electrons in its ground state?
1
2
3
4
0
Ans: A

18.
A)
B)
C)
D)
E)
The LUMO of the allylic radical has how many electrons in its ground state?
1
2
3
4
0
Ans: E

19.
A)
B)
C)
D)
E)
The HOMO of the allylic cation has how many electrons in its ground state?
1
2
3
4
0
Ans: B
Topic: Allylic Substitution Section: 13.3
20. What product(s) would you expect from the following substitution reaction of 14Clabeled propene?
14
CH2=CH-CH3
low conc. Cl2

500oC
A) 14CH2=CHCH2Cl alone
B) 14CH2=CHCH2Cl and CH2=CH14CH2Cl, in equal amounts
C) CH2=CH14CH2Cl alone
D) more 14CH2=CHCH2Cl, but a little CH2=CH14CH2Cl
E) more CH2=CH14CH2Cl, but a little 14CH2=CHCH2Cl
Ans: B
low conc. Cl2
13
A)
B)
C)
D)
E)
500oC
13
CH2=CHCH2Cl alone
13
CH2=CHCH2Cl and CH2=CH13CH2Cl, in equal amounts
CH2=CH13CH2Cl alone
more 13CH2=CHCH2Cl, but a little CH2=CH13CH2Cl
more CH2=CH13CH2Cl, but a little 13CH2=CHCH2Cl
Ans: B

22. What product(s) would you expect from the following substitution reaction?
* Cl2
?
500oC
Cl
Cl
Cl
*
I
A)
B)
C)
D)
E)
*
II
I
II
III
IV
More than one of the above
Ans: E
Cl
*
III
*
IV
Topic: Allylic Halogenation Section: 13.2 and 13.3

23. What is (are) the product(s) of the following reaction?
Cl2
?
400oC
Cl
Cl
Cl
I
A)
B)
C)
D)
E)
II
III
I
II
III
a mixture of I and II
a mixture of II and III
Ans: E

24. An unsaturated product results from the reaction of cyclohexene with which of these?
A) Br2/CCl4 at 25C
B) NBS/CCl4, ROOR
C) HCl, ROOR
D) HCl, no peroxides
E) More than one of these
Ans: B
N - b r o m o s u c c in im id e
14C
C H
C H
R O O R , C C l4
A) 14CH2=CHCH2Br alone
B) 14CH2=CHCH2Br and CH2=CH14CH2Br in equal amounts
C) CH2=CH14CH2Br alone
D) More 14CH2=CHCH2Br but a little CH2=CH14CH2Br
E) More CH2=CH14CH2Br but a little 14CH2=CHCH2Br
Ans: B
26.
A)
B)
C)
D)
E)
Treatment of 2-butene (cis or trans) with Cl2 at 400C would yield mainly:
CH2ClCHClCH2CH3
CH3CHClCH2CH3
CH3CH=CClCH3
CH3CH=CHCH2Cl and CH3CHClCH=CH2
CH3CHClCHClCH3
Ans: D
Topic: Synthesis of Allylic Halides Section: 13.2 and 13.3

27. Treatment of 2-butene (cis or trans) with N-bromosuccinimide in CCl4 would yield
mainly:
A) CH3CHBrCHBrCH3 alone
B) CH3CH=CBrCH3 alone
C) CH3CH=CHCH2Br alone
D) CH2BrCH2CH=CH2 and CH3CH=CHCH2Br
E) CH3CHBrCH=CH2 and CH3CH=CHCH2Br
Ans: E
Topic: Synthesis of Allylic Halides Section: 13.2 and 13.3
28. Treatment of 4-methylcyclohexene with N-bromosuccinimide in CCl4 would yield
mainly:
Br
Br
Br
Br
A)
B)
C)
D)
E)
I
II
III
IV
All of the above
Ans: E
II
III
IV
Topic: Synthesis of Allylic Halides Section: 13.2, 13.3 and previous chapters
29. Which of the following could be used to synthesize 3-bromopropene?
A)
25 oC
C H 3C H
C H 2
+
B r2
C C l4
R O O R
B)
C H 3C H
C H 2
+
N -b ro m o s u c c in im id e
C C l4
C) CH2=CHCH2OH + PBr3
D) More than one of these
E) None of these
Ans: D (BC)
Topic: Synthesis of Allylic Halides Section: 13.2, 13.3 and previous chapters
30.
A)
B)
C)
D)
E)
Which of the following could be used to synthesize 3-bromocyclopentene?

Cyclopentene + Br2, CCl4 , 25o
Cyclopentene + NBS, CCl4 (ROOR)
3-Cyclopentenol + PBr3
Both A) and B)
Both B) and C)
Ans: E

31. Which carbocation would be least stable?
I
A)
B)
C)
D)
E)
II
III
I
II
III
IV
V
Ans: E

32. Which carbocation would be most stable?
A)
B)
C)
D)
E)
Ans: C
IV
33. Which carbocation would be least stable?
A)
B)
C)
D)
E)
Ans: D
C H
I
A)
B)
C)
D)
E)
C H
C H
II
III
CH
CH
IV
I
II
III
IV
V
Ans: C

A)
B)
C)
D)
E)
I
II
III
IV
V
Ans: C
II
III
IV

36. Arrange these carbocations in order of expected increasing stability.
I
A)
B)
C)
D)
E)
II
III
IV
V < II < I < IV < III

V<I<II<IV<III
IV <I< II <V< III
IV < III < I < II < V
I < II < IV < III < V
Ans: B

37.
A)
B)
C)
D)
E)
The allyl cation has how many electrons in bonding molecular orbitals?
1
2
3
4
5
Ans: B

38. The allyl cation has how many bonding molecular orbitals?
A) 1
B) 2
C) 3
D) 4
E) 5
Ans: A
39. The allyl cation has how many molecular orbitals?
A) 1
B) 2
C) 3
D) 4
E) 5
Ans: C
Topic: Resonance Section: 13.5
40. Which is not an example of resonance?
CH2=CHCH2 .
II
CH2
CH2
CH2
CH3
III
+
.
IV
A)
B)
C)
D)
E)
. CH2CH=CH2
CH2=CHCHCH2CCl3
CH2CH=CHCH2CCl3
I
II
III
IV
None of these are examples of resonance.
Ans: C

41. Which is not a proper resonance structure for 1,3-butadiene?
A) CH2=CHCH=CH2
B)
CH
C)
CH
CH
CH
CH
C H
CH
CH
D)
CH
CH
CH
CH
E) All are correct

Ans: B
42. Which pair does not represent a pair of resonance structures?

H
H
H
and
H
H
II
H
H
III
IV
A)
B)
C)
D)
E)
H
H
and
H
H
C H
and
C H
and
H
CH
CH
I
II
III
IV
All of these represent pairs of resonance structures.
Ans: D

I
II
III
IV
A)
B)
C)
D)
E)
and
and
and
and
I
II
III
IV
Ans: D

I
II
III
IV
A)
B)
C)
D)
E)
and
and
and
and
I
II
III
IV
Ans: E

I
II
III
IV
A)
B)
C)
D)
E)
and
and
and
and
I
II
III
IV
Ans: E
Topic: Alkene Classification Section: 13.6
46. Select the structure of the conjugated diene.
I
A)
B)
C)
D)
E)
II
III
IV
I
II
III
IV
V
Ans: B

II
IV
A)
B)
C)
D)
E)
I
II
III
IV
V
Ans: C
III
II
IV
A)
B)
C)
D)
E)
III
I
II
III
IV
V
Ans: C

49. Select the structure of the isolated diene.
IV
A)
B)
C)
D)
E)
I
II
III
IV
V
Ans: D
III
II

50. Select the structure(s) of the conjugated diene(s).
II
A)
B)
C)
D)
E)
I and II
II and III
III and IV
I, II and V
V
Ans: C
IV
III

51.
A)
B)
C)
D)
E)
Which of the following dienes is a cumulated diene?

CH2=CHCH2CH2CH=CH2
CH2=CHCH=CHCH2CH3
CH3CH=C=CHCH2CH3
CH3CH=CHCH=CHCH3
CH3CH=CHCH2CH=CH2
Ans: C

52.
A)
B)
C)
D)
E)
Which of the following dienes is a cumulated diene?

CH2=CHCH2CH2CH2CH=CH2
CH2=CHCH=CHCH2CH2CH3
CH3CH=C=CHCH2CH2CH3
CH3CH=CHCH=CHCH2CH3
CH3CH2CH=CHCH2CH=CH2
Ans: C
53. Select the structure(s) of the conjugated diene(s).

O
II
A)
B)
C)
D)
E)
III
I and II
II and III
III and IV
I, II and V
V
Ans: B
Topic: Nomenclature Section: 4.5, 4.6 and 13.6

54.
What is an IUPAC name for
2,3-methylhept-2-en-4-yne
1,1,3-trimethylhex-3-yn-1-ene
1,1,3-trimethyl-3-hexyn-1-ene
2,3-dimethyl-2-hepten-4-yne
5,6-dimethyl-5-hepten-3-yne
Ans: D
Topic: Nomenclature Section: 4.5, 4.6 and 13.6
A)
B)
C)
D)
E)
55. A correct IUPAC name of the compound below is:

Br
A)
B)
C)
D)
E)
1-Bromo-1-methyl-2,5-cyclohexadiene
None of these
Ans: B
Topic: Nomenclature Section: 4.5, 4.6, 7.2 and 13.6
IV
56. What is an IUPAC name for this triene?

H
C H 3C H
A)
B)
C)
D)
E)
H H
2
C H
H
(2E,4Z,6E)2,4,6Nonatriene
(2Z,4E,6Z)2,4,6Nonatriene
(2E,4Z,6Z)2,4,6Nonatriene
(3Z,5Z,7E)3,5,7Nonatriene
(3Z,5E,7E)3,5,7Nonatriene
Ans: C

57. What is an IUPAC name for this triene?
A)
B)
C)
D)
E)
(2E,4Z,6E)3,4,7,8tetramethyl-2,4,6Nonatriene
(2Z,4E,6E)3,4,7,8tetramethyl-2,4,6Nonatriene
(2E,4Z,6E)2,3,6,7tetramethyl-3,5,7Nonatriene
(2E,4Z,6E) 2,3,6,7tetramethyl-3,5,7Nonatriene
(2E,4E,6E)3,4,7,8tetramethyl-2,4,6Nonatriene
Ans: E
Topic: Bond Lengths Section: 13.7

58.
A)
B)
C)
D)
E)
Which compound would have the shortest carbon-carbon single bond?

CH3CH3
CH2=CHCH3
HCCCCH
CH2=CHCCH
CH2=CHCH=CH2
Ans: C

59. Which compound would have the shortest carbon-carbon single bond?
A)
B)
C)
D)
E)
CHCCH=CHCH2CH3
CH2=CHCH=CHCH3
HCCCH2CCCH3
CH2=CHCCCH2CH3
CH3CCCCCH3
Ans: E

60. Which carbon-carbon bond in the following compound would you expect to be shortest?
H
A)
B)
C)
D)
E)
CH
I II
I
II
III
IV
V
Ans: A
CH
III
CH2
IV
CH3

61. Which carbon-carbon bond in the following compound would you expect to be longest?
H
A)
B)
C)
D)
E)
I
I
II
III
IV
V
Ans: E
CH
II
CH
III
CH2
IV
CH3

62.
A)
B)
C)
D)
E)
1,3-Pentadiene has how many bonding molecular orbitals?

1
2
3
4
0
Ans: B

63.
A)
B)
C)
D)
E)
1,3-butadiene has how many bonding molecular orbitals?

1
2
3
4
0
Ans: B

64.
A)
B)
C)
D)
E)
1,3-Pentadiene has how many antibonding molecular orbitals?

1
2
3
4
0
Ans: B

65.
A)
B)
C)
D)
E)
1,3-butadiene has how many electrons in its ground state bonding molecular orbitals?
1
2
3
4
0
Ans: D

66. 1,3-butadiene has how many electrons in its ground state antibonding molecular
orbitals?
A) 1
B) 2
C) 3
D) 4
E) 0
Ans: E
67.
A)
B)
C)
D)
E)
The HOMO of 1,3-pentadiene has how many electrons in its ground state?
1
2
3
4
0
Ans: B
68.
A)
B)
C)
D)
E)
The LUMO of 1,3-pentadiene has how many electrons in its ground state?
1
2
3
4
0
Ans: E

69.
A)
B)
C)
D)
E)
The HOMO of 1,3-pentadiene has how many electrons in its excited state?
1
2
3
4
0
Ans: A

70.
A)
B)
C)
D)
E)
The LUMO of 1,3-pentadiene has how many electrons in its excited state?
1
2
3
4
0
Ans: E

71.
A)
B)
C)
D)
E)
Which of the following dienes would you expect to be the most stable?
CH3CH=CHCH=CHCH3
CH3CH=CHCH2CH=CH2
CH2=CHCH2CH2CH=CH2
CH2=CHCH(CH3)CH=CH2
CH3CH=C=CHCH2CH3
Ans: A

72. Which of the following dienes would you expect to be the most stable?
A) CH3CH2CH=CHCH2CH=CHCH3
B) CH3CH=CHCH=CHCH2CH3
C) CH2=CHCH2CH2CH2CH=CH2
D) CH2=CHCH=CHCH2CH2CH3
E) CH3CH2CH=C=CHCH2CH3
Ans: B
Topic: Stability (Alkenes, Cations, Radicals Section: 13.8
73. Which of the following compounds would be the most stable?
I
A)
B)
C)
D)
E)
II
III
IV
I
II
III
IV
They are all of equal stability.
Ans: A

74. Which diene would be least stable?
I
A)
B)
C)
D)
E)
II
III
IV
I
II
III
IV
V
Ans: C
Topic: Heat of Hydrogenation Section: 13.8

75. Which alkene would you expect to have the highest heat of hydrogenation?
A)
B)
C)
D)
E)
Ans: A
76.
A)
B)
C)
D)
E)
Which of the following dienes would you expect to be the most stable?
CH3CH2CH=CHCH2CH=CHCH3
CH3CH=CHCH=CHCH2CH3
CH3CH=C(CH3)CH=CHCH2CH3
Ans: E

77.
A)
B)
C)
D)
E)
Which of the following dienes would you expect to be the least stable?
CH3CH2CH=CHCH2CH=CHCH3
CH3CH=CHCH=CHCH2CH3
CH3CH=C(CH3)CH=CHCH2CH3
Ans: C

78. Considering both configurational and conformational factors, select the most stable
form of 2,4-hexadiene.
C H
C H
H
H
C H
I
A)
B)
C)
D)
E)
C H
C H
H
3
C H
II
C H
C H
C H
IV
III
C H
I
II
III
IV
V
Ans: A

79. Considering both configurational and conformational factors, select the least stable form
of 2,4-hexadiene.
C H
C H
H
H
C H
I
A)
B)
C)
D)
E)
I
II
III
IV
V
Ans: E
C H
II
C H
H
3
C H
III
C H
C H
IV
H
3
C H
C H
3

80. Which alkene would you expect to be most stable?
A) CH2=CHCH2CH2CH=CH2
H
B) C H 2 C H C H 2
C
C) C H
H
C H 2C H
D)
H
C H
C
H
H
C
C H3
CH2
H
C
H
E) C H 3
C H
H
H
C
H
C
C
CH
Ans: E
81. Arrange these hexadienes in order of expected decreasing stability.
II
IV
A)
B)
C)
D)
E)
III
V > II > I > III > IV

III > IV > II > I > V
IV > III > II > V > I
IV > III > I > II > V
I > II > IV > III > V
Ans: D

82. Arrange these hexadienes in order of expected increasing stability.
II
IV
A)
B)
C)
D)
E)
V < II < I < III < IV

III < IV < II < I < V
IV < III < II < V < I
IV < III < I < II < V
I < II < IV < III < V
Ans: A
III
83. Which alkene would you expect to have the smallest heat of hydrogenation?
H
B) C H 2 C H C H 2
C
C) C H
C H 2C H
D)
C H
H
C
H
C
E) C H
C H3
CH2
C H
H
H
H
C
C
CH
Ans: E
84. Which alkene would you expect to have the smallest heat of hydrogenation?
A)
B)
C)
D)
E)
Ans: E
85. Which alkene would you expect to have the lowest heat of hydrogenation?
II
IV
III
A)
B)
C)
D)
E)
I
II
III
IV
V
Ans: A

86. Estimate the stabilization energy for 1,3-butadiene using the heats of hydrogenation in
Table 1.
Table 1.
Heats of Hydrogenation for Selected Compounds
Compound
A)
B)
C)
D)
E)
1-Butene
1-Pentene
1,3-Butadiene
trans-1,3-Pentadiene
13 kJ mol-1
15 kJ mol-1
28 kJ mol-1
239 kJ mol-1
112 kJ mol-1
Ans: B
Moles H2
H(kJ mol-1)
1
1
2
2
-127
-126
-239
-226
87. Estimate the stabilization energy for 1,3-pentadiene using the heats of hydrogenation in
Table 1.
Table 1.
Compound
A)
B)
C)
D)
E)
1-Butene
1-Pentene
trans-2-pentene
1,3-Butadiene
trans-1,3-Pentadiene
13 kJ mol-1
15 kJ mol-1
28 kJ mol-1
239 kJ mol-1
112 kJ mol-1
Ans: B
Moles H2
H(kJ mol-1)
1
1
1
2
2
-127
-126
-115
-239
-226

88. Estimate the stabilization energy for 1,3-cyclohhexadiene using the heats of
hydrogenation in Table 1.
Table 1.
Compound
A)
B)
C)
D)
E)
Cyclohexene
1,4-Cyclohexadiene
1,3-Cyclohexadiene
1,5-Hexadiene
13 kJ mol-1
21 kJ mol-1
8 kJ mol-1
120 kJ mol-1
112 kJ mol-1
Ans: C
Moles H2
H(kJ mol-1)
1
2
2
2
-120
-240
-232
-253
Topic: UV-Vis Spectroscopy Section: 13.9

89. Which compound would have a UV absorption band at longest wavelength?
C H C H
C H
CH C H
C H
II
C H 2C H
C H
IV
A)
B)
C)
D)
E)
C H
III
C H
C H C H
I
II
III
IV
V
Ans: B

90.
A)
B)
C)
D)
E)
Select the most energetically favorable UV transition for 1,3-butadiene.

n
*
n
*
2
3*

*
1
4*
Ans: C
C HC H
91. Which compound would have a UV absorption band at longest wavelength?

C H
C H C H
C H
C H
C H C H
C H
II
C H 2C H 2C H
C H
C H C H
C H
III
C H
C H C H
IV
A)
B)
C)
D)
E)
C H
C H
I
II
III
IV
V
Ans: A

92. Which of these symbols is used in connection with the intensity of absorption in the UVvisible region?
A)
B)
C)
D)
E)
Ans: C
Topic: Conjugate Addition Reactions Section: 13.10
93. Ignoring stereochemistry, the 1:1 reaction of bromine with 1,3-cyclohexadiene at 25C
in the dark and in the absence of peroxide forms which of these?
Br
Br
Br
Br
Br
I
A)
B)
C)
D)
E)
II
Br
III
I
II
III
IV
Both I and II
Ans: E
Br
IV
94. Which of the following dienes might react with bromine in CCl4 to yield 2,5-dibromo-3hexene?
B) CH2=CHCH=CHCH2CH3
C) CH3CH=C=CHCH2CH3
D) CH3CH=CHCH=CHCH3
E) CH3CH=CHCH2CH=CH2
Ans: D

95. Indicate which products would be obtained from the chlorination of 1,5-hexadiene at
high temperature (500C), using a 1:1 mole ratio of the reactants.
C lC H 2 C H C H 2 C H 2 C H
C H
C lC H 2 C H
C H C H
C H C H 2C l
C l
II
C lC H 2 C H
C H C H 2C H
C H
III
C H
C H C H 2C H C H
C l
IV
A)
B)
C)
D)
E)
I and II
II and III
III and IV
IV and V
V and I
Ans: C
C H
C lC H 2 C H C H 2 C H 2 C H C H 2 C l
Cl
C l
Topic: 1,2 Reactions of Conjugated Dienes Section: 13.10

96. Which reagent would convert 1,3-pentadiene into 3-penten-2-ol?
A)
B)
C)
D)
E)
KMnO4/-OH
OsO4
H2O2, then H3O+
Cl2/H2O
H3O+
Ans: E
Topic: 1,2 Reactions of Conjugated Dienes Section: 13.10

97.
A)
B)
C)
D)
E)
Which reagent would convert 1,3-octadiene into 3-octen-2-ol?

KMnO4/-OH
OsO4
H2O2, then H3O+
Cl2/H2O
H3O+
Ans: E

98. Which is the only compound which can be completely ruled out as a product of the
reaction of 1,3-butadiene with HCl?
A) (S)-3-chloro-1-butene
B) (R)-3-chloro-1-butene
C) (E)-1-chloro-2-butene
D) (Z)-1-chloro-2-butene
E) (Z)-2-chloro-2-butene
Ans: E
Topic: Multistep Synthesis Section: 13.10 and previous chapters
99. How could the following synthesis be carried out?
C H 2C H
A)
B)
C)
D)
E)
(1) Br2/CCl4; (2) CH3CH2MgCl, ether; (3) CH3ONa/CH3OH

(1) HBr, 80C; (2) (CH3CH2)2CuLi, ether
(1) HBr, 80C; (2) Mg, ether; (3) CH3CH2OH, then H3O+
All of the above
Ans: B
Topic: Multistep Reaction Sequence Section: 13.10 and previous chapters
100. How could the following synthesis be carried out?
A)
B)
C)
D)
E)
(1) Br2/CCl4; (2) CH3MgCl, ether; (3) CH3ONa/CH3OH

(1) HBr (1 eq); (2) (CH3)2CuLi, ether
(1) HBr (1eq); (2) Li, ether; (3) CuI; (4) CH3Br
All of the above
Ans: C
Topic: Reaction Mechanisms and Control Section: 13.10A

101.
A)
B)
C)
D)
E)
A thermodynamically-controlled reaction will yield predominantly:

the more/most stable product.
the product whose formation requires the smallest free energy of activation.
the product that can be formed in the fewest steps.
the product that is formed at the fastest rate.
the product which possesses the greatest potential energy.
Ans: A

102.
A)
B)
C)
D)
E)
An equilibrium-controlled reaction will yield predominantly:

the more/most stable product.
the product that is formed at the fastest rate.
the product which possesses the greatest potential energy.
Ans: A

103.
A)
B)
C)
D)
E)
A reaction under kinetic (or rate) control will yield predominantly:

the most stable product.
the product with the greatest potential energy.
the product with the least potential energy.
Ans: C
104. The accompanying diagram, which describes the fate of the intermediate in a reversible
reaction, implies that:
B
A
A)
B)
C)
D)
E)
reaction coordinate
the less stable product forms more rapidly.
the more stable product forms more rapidly.
product B will predominate at equilibrium.
the intermediate has a short lifetime.
No conclusions can be drawn as to either reaction rate or product stability.
Ans: B

105. The accompanying diagram, which describes the fate of the intermediate in a reversible
reaction, implies that:
A)
B)
C)
D)
E)
the less stable product forms more rapidly.

the more stable product forms more rapidly.
product B will predominate at equilibrium.
the intermediate has a short lifetime.
No conclusions can be drawn as to either reaction rate or product stability.
Ans: A

106. The accompanying diagram implies that:
B
A
reaction coordinate
A) the formation of B from A would be favored at high temperature.
B) the more stable product forms more rapidly from the intermediate species.
C) the formation of B from the intermediate is the rate-limiting step in the transformation
of A into B
D) the formation of B from A is not a concerted reaction.
E) All of the above statements are true.
Ans: E
Topic: Diels-Alder Reaction Section: 13.11

107.
A)
B)
C)
D)
E)
Which is an untrue statement concerning the Diels-Alder reaction?

The reaction is a syn addition.
The diene must be in the s-cis conformation to react.
Most Diels-Alder reactions are reversible.
Generally, the adduct formed most rapidly is the exo product.
Electron donating groups on the diene and electron withdrawing groups on the
dieneophile favor adduct formation.
Ans: D
108. Which of these dienes can undergo the Diels-Alder reaction?

A)
B)
C)
D)
E) All of the above can undergo the Diels-Alder reaction.

Ans: A
109. Which of these dienes can undergo the Diels-Alder reaction?
A)
B)
C)
D)
E)
Ans: B
110. Which of the following can undergo the Diels Alder reaction?
II
III
IV
A)
B)
C)
D)
E)
I and II
II and III
III and IV
I, II and V
V
Ans: C

111. From the standpoint of reactivity, which is the poorest choice of dienophile to react with
2,3-dimethyl-1,3-butadiene in a Diels-Alder reaction?
O
II
H3CO
III
O
O
H3CO
OCH3
IV
A)
B)
C)
D)
E)
I
II
III
IV
V
Ans: B
OCH3
O

112. What is the product of the following reaction?
C H
C H
C O C H
C O C H
C H 3C
O
C
C C H
C O C H
C O C H
?
3
II
C O C H
C O C H
III
C O C H
C O C H
IV
A)
B)
C)
D)
E)
I
II
III
IV
V
Ans: A
C O C H
C O C H

113. Which would be the best synthesis of the following compound?
C O 2C H
C O 2C H 3
C O 2C H
C O 2C H
C O 2C H
+
C O 2C H
C H 3O 2C
II
C O 2C H
C O 2C H
+
IV
I
II
III
IV
V
Ans: B
C O 2C H
A)
B)
C)
D)
E)
III
2 H C O 2C H
V

114. Which reaction would produce the following compound?
H
C O 2C H
C O 2C H
C O 2C H
C O 2C H
C O 2C H
+
C H 3O 2C
II
C O 2C H
C O 2C H
C O 2C H
C O 2C H
+
III
A)
B)
C)
D)
E)
I
II
III
IV
None of the above
Ans: D
IV

115. Which of the following pairs of compounds could be used as the basis for a Diels-Alder
synthesis of the compound shown below?
C O 2C H
2 C H 3C H
C H C H
II
III
C H 3C H
C H
C O 2C H
C H
C H C O 2C H
+
C O 2C H
IV
A)
B)
C)
D)
E)
I
II
III
IV
Ans: D
C H
C H C O 2C H

O
N
COOCH3
COOCH3
O
N
H3CO
OCH3
II
H3CO
OCH3
+
O
IV
Ans: A
+
III
A)
B)
C)
D)
E)
NH2
COOCH3
H3COOC
I
II
III
IV
V
HN
N
O

O
O
O
O
I
II
III
O
O
IV
A)
B)
C)
D)
E)
Ans: B
I
II
III
IV
V

O
O
O
+ 2
O
I
II
III
O
O
2
O
IV
A)
B)
C)
D)
E)
Ans: B
I
II
III
IV
V

119.
A)
B)
C)
D)
E)
does not undergo the Diels-Alder reaction because:

ring systems cannot function as the diene component.
it cannot adopt the s-cis conformation.
it lacks electron-withdrawing groups.
it lacks strong electron-releasing groups.
the two double bonds are farther apart than in a non-cyclic conjugated system.
Ans: B

120.
A)
B)
C)
D)
E)

Ans: A

121.
A)
B)
C)
D)
E)

Ans: B
122.
A)
B)
C)
D)
E)

Ans: B

123.
A)
B)
C)
D)
E)

the two double bonds are further apart than in a non-cyclic conjugated system.
Ans: B

124. Which of these dienes is the most reactive in the Diels-Alder reaction?
A)
B)
C)
D)
E)
Ans: C
125. Which of the following dieneophiles is most reactive in a Diels-Alder reaction:
O
O
O
I
II
A)
B)
C)
D)
E)
IV
III
I
II
III
IV
V
Ans: C

126. Which of the following dieneophiles is most reactive in a Diels-Alder reaction:
OCH3
A)
B)
C)
D)
E)
II
III
I
II
III
IV
V
Ans: D
NC
CN
NC
CN
IV
OCH3
V
127. Which diene and dienophile would you choose to synthesize the following compound?
H
C O C H
and
C H
C H
and
and
H C
C C O C H
II
O
C H
C H C O C H
and
3
III
A)
B)
C)
D)
E)
I
II
III
IV
None of these
Ans: C
O
C H
IV
C H C O C H
H
O
C O C H
and
C H
C H
and
H C
and
II
O
C H
C H C O C H
and
C H
III
A)
B)
C)
D)
E)
C C O C H
C H C O C H
IV
I
II
III
IV
None of these
Ans: B

129. Which diene would be least reactive toward Diels-Alder addition of maleic anhydride?
C H
C H
C H
CH
C H
C H
I
II
III
IV
V
Ans: E
CH
CH
C H
II
IV
A)
B)
C)
D)
E)
C H
3
2
III
C H
C H

130. What would be the product of the following reaction?
O
C H
C H
A)
B)
C)
D)
E)
O
3
C
C H
C HC CH
heat
C H
C H
II
I
II
III
IV
All of these
Ans: C
III
C
C H
IV
C H
H
+
O
+
III
II
+
IV
A)
B)
C)
D)
E)
I
II
III
IV
None of these
Ans: A
+
O
V
132. Which of the following would afford a synthesis of the following compound?
C HO
2 C H 3C H
II
C H 3C H
CH O
CH C H
C H
+
C H O
A)
B)
C)
D)
E)
III
C H
C H C H O
IV
C H
C H C H O
I
II
III
IV
None of these
Ans: D

133. What is the product of the following Diels-Alder cycloaddition reaction:
O
+
O
O
A)
B)
C)
D)
E)
I
II
III
IV
None of these
Ans: D
II
III
O
IV

CHO
CHO
CHO
O
III
H
+
IV
A)
B)
C)
D)
E)
I
II
III
IV
None of these
Ans: C
II

CHO
OHC
CHO
+
O
O
II
+
O
IV
A)
B)
C)
D)
E)
I
II
III
IV
None of these
Ans: D
O
III

CHO
CHO
CHO
O
III
H
+
IV
A)
B)
C)
D)
E)
I
II
III
IV
None of these
Ans: C
II

137. Which diene would you expect to react most rapidly with maleic anhydride?
O
C H
C H
C H 3C
C H
C H
C H 3C
O
I
A)
B)
C)
D)
E)
II
III
IV
I
II
III
IV
V
Ans: D

138. Which of these conjugated dienes can undergo a Diels-Alder reaction?
C H
(C H 3)3C
C H
A)
B)
C)
D)
E)
II
I
II
III
IV
V
Ans: C
III
IV
C H
C (C H 3)3
139. Which of these conjugated dienes can undergo a Diels-Alder reaction?

O
O
I
A)
B)
C)
D)
E)
II
III
IV
I
II
III
IV
All of the above
Ans: E

140. Which of these dienes can undergo a Diels-Alder reaction?
II
IV
A)
B)
C)
D)
E)
I and V
I, II and V
III
IV
III and IV
Ans: D
III
O
H
C O C H
O
O
CO C H
and
and
and
H C
CO C H
II
O
C H
C H
C O C H
III
A)
B)
C)
D)
E)
O
3
and
O
C H
C H
C O C H
IV
I
II
III
IV
None of these
Ans: C

S
CN
CN
CN
S
+
S
+
S8
NC
CN
II
III
S
+
IV
A)
B)
C)
D)
E)
I
II
III
IV
None of these
Ans: B
NC
CN
CN
NC
Topic: Diels-Alder Reaction

Section: 13.11
H
CHO
H
CHO
CHO
CHO
CHO
CHO
II
III
OHC
CHO
CHO
A)
B)
C)
D)
E)
IV
I and VI
II and V
III and IV
IV and V
I and III
Ans: E
CHO
VI

CHO
H
H
CHO
CHO
CHO
CHO
CHO
II
III
OHC
CHO
CHO
IV
A)
B)
C)
D)
E)
CHO
VI
I and VI
II and V
III and IV
IV and V
I and III
Ans: A

145. Which compounds could be used in a Diels-Alder synthesis of
C H
C O 2C H
?
C H
C H
C H
C H
C H
A)
B)
C)
D)
I
I and III
I and IV
II and III
II and IV
Ans: C
C H
C H C O 2C H
H C
C C O 2C H
II
III
IV

146. Which is the major product of the following reaction?
O
H
+
H
C
C
O H
C
O H
H
C O 2H
C O 2H
A)
B)
C)
D)
E)
I
II
III
IV
None of these
Ans: D
H
H
H
C O 2H
H
II
C O 2H
C O 2H
C O 2H
H
C O 2H
III
C O 2H
IV

O
147. Which is the major product of the following

reaction?
H
C
+
HO2C
O H
O H
CO2H
H
H
H
H
C O 2H
C O 2H
C O 2H
H
C O 2H
C O 2H
C O 2H
C O 2H
A)
B)
C)
D)
E)
II
C O 2H
III
IV
I
II
III
IV
None of these
Ans: A

CHO
+
CHO
H
CHO
H
CHO
I
A)
B)
C)
D)
E)
I
II
III
IV
V
Ans: A
CHO
H
CHO
H
II
H
CHO
CHO
H
III
CHO
H
H
CHO
IV
H
CHO
H
CHO

H
CHO
H
CHO
I
A)
B)
C)
D)
E)
CHO
H
CHO
H
II
CHO
OHC
H
CHO
CHO
H
III
CHO
CHO
IV
CHO
CHO
I
II
III
IV
V
Ans: D

H
CHO
H
CHO
I
A)
B)
C)
D)
E)
I
II
III
IV
V
Ans: C
CHO
H
CHO
H
II
CHO
CHO
III
CHO
IV
CHO

O
C O C H
O
O
C O C H
and
and
and
H C
O
C H
C H
C O CH
and
C H
IV
I
II
III
IV
None of these
Ans: B
Which of these dienes is the most reactive in the Diels-Alder reaction?

1,3-Butadiene
1,4-Pentadiene
2,3,-Dimethyl-1,3-butadiene
1,2-Butadiene
1,4-Cyclohexadiene
Ans: C

153.
A)
B)
C)
D)
E)

152.
A)
B)
C)
D)
E)
C O C H
II
III
A)
B)
C)
D)
E)
Which of these dienes can undergo the Diels-Alder reaction?

1,3-Pentadiene
1,4-Pentadiene
1,2-Butadiene
1,4-Cyclohexadiene
All of the above can undergo the Diels-Alder reaction
Ans: A
C H
C O C H

154.
A)
B)
C)
D)
E)
Which of these dienes can undergo the Diels-Alder reaction?

1,2-Heptadiene
1,3-Heptadiene
1,4-Heptadiene
1,5-Heptadiene
1,6-Heptadiene
Ans: B
155. How would you synthesize:

H
O
C O C H
O
O
1 ,3 -C y c lo h e x a d ie n e
C H
C H C O C H 3,
th e n
II
R C O O H
O
th e n
R CO O H ,
C H
C H C O C H 3,
O
C O C H
III
C H
CH
O
O
IV
C H
C H C O C H 3,
C H
C H
C H
th e n
C H
O
C O C H
A)
B)
C)
D)
E)
I
II
III
IV
V
Ans: A
SHORT ANSWER QUESTIONS

Topic: General Section: 13.1
156. Systems that have a p orbital on an atom adjacent to a double bond are called
______________ systems.
Ans: conjugated unsaturated
157. The hydrogen atom on a saturated (sp3) carbon adjacent to a double bond is called an
______________ hydrogen.
Ans: allylic
158. The hydrogen atom on a carbon that is part of a double bond is called a ___________
hydrogen.
Ans: vinyl or vinylic
159. Allylic radicals are ___________ stable than tertiary radicals.
Ans: more
160. Vinyl cations are _____________ stable than tertiary cations.
Ans: less
161. There are three types of polyenes (molecules containing two or more double bonds).
They are: _________________.
Ans: conjugated, cumulated, isolated
162. Polyenes in which single and double bonds alternate along the carbon chain are called
___________.
Ans: conjugated
Topic: Nomenclature Section: 4.5, 4.6, 5.7, and 13.6
163. Draw the structural formula for (R)-5-bromo-2,5-dimethyl-1,3-cyclopentadiene, clearly
indicating stereochemical details.
CH3
Ans:
Br

164. Draw the structural formula for (2E,4Z,6E)3,4,7,8tetramethyl-2,4,6nonatriene,
clearly indicating stereochemical details.
Ans:

165. Draw the structural formula for (2Z,4Z,6Z)-3,4,8-trimethyl-2,4,6-nonatriene, clearly
indicating stereochemical details.
Ans:

166. UV-vis spectroscopy can be used to indicate whether _________________ is present.
Ans: conjugation
167. When the product distribution for a particular reaction reflects the relative stabilities of
the products, the reaction is said to be under ______________ control.
Ans: thermodynamic
168. When the product distribution for a particular reaction reflects the relative rate at which
the products are formed, the reaction is said to be under _______________ control.
Ans: kinetic
169. A thermodynamically-controlled reaction will yield predominantly:___________.
Ans: the more/most stable product.
170. A reaction under kinetic (or rate) control will yield predominantly:___________.
Ans: the product whose formation requires the smallest free energy of activation.
171. Conjugated dienes routinely undergo 1,2 and 1,4 addition reactions with a variety of
electrophilic reagents; this suggests that ___________ are likely intermediates during
these reactions.
Ans: allylic carbocations
Topic Conjugate Addition Section: 13.10

172. Predict the product(s) of the following reaction:
DCl
Ans:
Cl
+
D
D
Cl

173. The Diels-Alder reaction is a cycloaddition between a conjugated ________ and a
___________.
Ans: diene; dienophile
174. Stereochemically speaking, the Diels-Alder reaction is ___________ and occurs with
___________ of the dienophile stereochemistry.
Ans: stereospecific; retention
Topic: Diels-Alder Reactions Section: 13.11
175. During Diels-Alder reactions, when two stereoisomer products, exo and endo, are
possible, the ___________ product is typically obtained as the major product.
Ans: endo
Section: 13.11
176. What reagents would be needed to synthesize the following substance via the DielsAlder reaction? Give stereochemical details, as relevant.
O
O
O
O
Ans:
+
O
O
Section: 13.11
177. Which diene and dienophile would you use to prepare the following molecule using a DielsAlder cycloaddition reaction:
o
O
Ans:
O
O
Section: 13.11
CHO
CHO
Ans:
+
OHC
CHO
Section: 13.11
179. The first step in the total synthesis of synthetic cholesterol involves production of the
intermediate structure shown. Which combination of diene and dieneophile will result in
its preparation?
O
H3CO
O
Ans:
O
+
H3CO
O
Section: 13.11
180. The structure below is an intermediate along the way to the production of synthetic
morphine. It is produced through a Diels-Alder cycloaddition reaction. Which
combination of diene and dieneophile will result in its preparation?
O
O
CN
H3CO
OCH3
Ans:
O
O
+
H3CO
OCH3
CN

181. What combination of diene and dieneophile can be used to prepare the following
compound through a Diels-Alder cycloaddition reaction:
O
N
COOCH3
COOCH3
Ans:
O
O
N
H3CO
OCH3
+
O
Topic Diels-Alder Reaction Section: 13.11

182. Predict the product of the following Diels-Alder cycloaddition reaction:
S
+ NC
CN
Ans:
S
CN
CN
Topic Diels-Alder Reaction Section: 13.11

183. Steroids are naturally occurring polycyclic compounds classified as lipids. The DielsAlder reaction has been widely used in their preparation. Shown below is a precursor
molecule used in a total steroid synthesis. What combination of diene and dieneophile can
be used to prepare this compound through the use of a Diels-Alder cycloaddition reaction.
O
H3CO
Ans:
O
+
H3CO
Topic: Diels-Alder Mechanism Section: 13.11

184. Draw arrows to indicate the electron flow for the following intramolecular Diels-Alder
cycloaddition reaction:
Ph
O
O
O
N
Ph
Ans:
N
O
O
O
N
Ph
Ph
Topic: Diels-Alder Mechanism Section: 13.11

185. Draw arrows to indicate electron movement that explains the formation of the products
shown for the following retro-Diels-Alder reaction:
o
CN
CN
CN
CO2
CN
Ans:
o
CN
CN
CN
CO2
CN

186. The compound shown below undergoes a retro-Diels-Alder cycloaddition reaction to yield
carbon dioxide and another compound. Predict the structure of the other compound
formed.
O
O
CN
CN
Ans:
CN
CN
CO2
Section: 13.11
187. The alkaloid colchicine is used in the treatment of gout. The first synthetic colchine
involved the preparation of the key intermediate shown. Which combination of diene and
dieneophile will result in its preparation?
H3CO
Cl
H3CO
O
O
OCH3
Ans:
Cl
H3CO
H3CO
O
OCH3
O
O
O
Section: 13.11
CN
CN
Ans:
+
NC
CN
Topic: Multistep Reactions Section: 13.11 and previous chapters

189. Complete the following sequence of reactions, giving structural details of all key
intermediates.
O
heat
H2
Ni
Ans:
heat
H2, Ni
O
+
+
O
O
+
O
Topic: Multistep Reactions Section: 13.11 and previous chapters
intermediates.
i) cis-CH3CH=CHCHO
?
ii) CH3CH2MgBr
iii) H3O+
Ans:
H
CHO
CH3
H
i) CH3CH2MgBr
CH3
H
ii) H3O
HO
Topic: Multistep Reactions Section: 13.2, 13.3, 13.11 and previous chapters
intermediates.
i) NBS
ii) (CH3)3COK, (CH3)3COH, heat
iii) trans CH3CH=CHCHO
Ans:
Br
NBS
(CH3)3COK,
(CH3)3COH,
heat
O

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Chapter Thirteen

Topic: Stability (Alkenes, Cations, Radicals) Section: 13.2

Topic: Stability (Alkenes, Cations, Radicals) Section: 13.2

Topic: Stability (Alkenes, Cations, Radicals) Section: 13.2

Topic: Stability (Alkenes, Cations, Radicals) Section: 13.2

Topic: Stability (Alkenes, Cations, Radicals) Section: 13.2

Which hydrogen atom(s) of

is/are most susceptible to abstraction

Topic: Stability (Alkenes, Cations, Radicals) Section: 13.2

Which hydrogen atom(s) of

is/are least susceptible to

Topic: Allylic Halogenation Section: 13.2

Which set of conditions does not result in allylic halogenation of an alkene?

Topic: Allylic Halogenation Section: 13.2

Topic: Multistep Reactions Section: 13.2

Topic: Allylic Halogenation Section: 13.2 and chapter 10

The allyl radical has how many bonding molecular orbitals?

Topic: Molecular Orbitals Section: 13.3

Topic: Molecular Orbitals Section: 13.3

Topic: Molecular Orbitals Section: 13.3

The allyl radical has how many molecular orbitals?

Topic: Molecular Orbitals Section: 13.3

Topic: Molecular Orbitals Section: 13.3

Topic: Molecular Orbitals Section: 13.3

Topic: Allylic Substitution Section: 13.3

low conc. Cl2

Topic: Allylic Substitution Section: 13.3

Topic: Allylic Halogenation Section: 13.2 and 13.3

Topic: Allylic Halogenation Section: 13.2 and 13.3

Topic: Synthesis of Allylic Halides Section: 13.2 and 13.3

Which of the following could be used to synthesize 3-bromocyclopentene?

Topic: Stability (Alkenes, Cations, Radicals) Section: 13.4

Topic: Stability (Alkenes, Cations, Radicals) Section: 13.4

33. Which carbocation would be least stable?

Topic: Stability (Alkenes, Cations, Radicals) Section: 13.4

Topic: Stability (Alkenes, Cations, Radicals) Section: 13.4

V < II < I < IV < III

Topic: Molecular Orbitals Section: 13.4

Topic: Molecular Orbitals Section: 13.4

40. Which is not an example of resonance?

Topic: Resonance Section: 13.5

E) All are correct

42. Which pair does not represent a pair of resonance structures?

Topic: Resonance Section: 13.5

43. Which pair does not represent a pair of resonance structures?

Topic: Resonance Section: 13.5

Topic: Resonance Section: 13.5

Topic: Alkene Classification Section: 13.6

46. Select the structure of the conjugated diene.

Topic: Alkene Classification Section: 13.6

Topic: Alkene Classification Section: 13.6

48. Select the structure of the conjugated diene.

Topic: Alkene Classification Section: 13.6

Topic: Alkene Classification Section: 13.6

Topic: Alkene Classification Section: 13.6

Which of the following dienes is a cumulated diene?

Topic: Alkene Classification Section: 13.6

Which of the following dienes is a cumulated diene?