CH 12

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

Chapter Number: 12
Question type: Multiple choice
1) Which of the following resonance structures is not a significant contributor to the hybrid for
the carbonyl group?
C O C O C O
I II III
a) I
b) II
c) III
d) Neither II nor III is important.
e) All are significant contributors.
Answer: B
Topic: General Carbonyl Information

Section: 12.1
Difficulty Level: Easy
2) When nucleophilic addition to a carbonyl group occurs, the carbon attacked undergoes this
hybridization change:
a) sp2  sp3

b) sp  sp2
c) sp  sp3
d) sp3  sp2
e) sp2  sp
Answer: A
Topic: General Carbonyl Information

Section: 12.1
3) The following transformation would be considered a(n)?
1
OH O
a) Reduction
b) Oxidation
c) Addition
d) Elimination
e) Rearrangement
Answer: B
Topic: Oxidation-Reduction
Section: 12.2
a) Reduction
b) Oxidation
c) Addition
d) Elimination
e) Rearrangement
Answer: A
Section: 12.2
a) Reduction
2
b) Oxidation
c) Addition
d) Elimination
e) Rearrangement
Answer: A
Section: 12.2

O O
H OH
a) Reduction
b) Oxidation
c) Addition
d) Elimination
e) Rearrangement
Answer: B
Section: 12.2
a) Reduction
b) Oxidation
c) Addition
d) Elimination
e) Rearrangement
Answer: A
Section: 12.2
3
a) Reduction
b) Oxidation
c) Addition
d) Elimination
e) Rearrangement
Answer: B
Section: 12.2
9) Which reaction is an oxidation?
a) RCHO  RCO2H

b) RCH2OH  RCHO
c) RCH2OH  RCO2H
d) None of these choices.
e) All of these choices.
Answer: E
Section: 12.2
10) Which of these transformations cannot be classified as a reduction?
a) RCH2Cl  RCH3

b) RCH=CH2  RCH2CH3
c) RCOOH  RCH2OH
O
d) RCOR' RCH2OH + R'OH

e) All of these are reductions.
4
Answer: E
Section: 12.2
11) List the following compounds in order of increasing level of oxidation:

OH O
II III
I
a) I, II, III
b) I, III, II
c) II, I, III
d) III, II, I
e) III, I, II
Answer: E
Section: 12.2
Difficulty Level: Medium

OH NH
II III
I
a) I, II, III
b) I, III, II
c) II, I, III
d) III, I, II
e) III, II, I
Answer: D
Section: 12.2
5
Cl NH NH2
II III
I
a) I, II, III
b) III, II, I
c) II, I, III
d) III, I, II
e) I, III, II
Answer: A
Section: 12.2

O
I II III
a) I, II, III
b) III, II, I
c) II, I, III
d) III, I, II
e) I, III, II
Answer: D
Section: 12.2
6
a) I, II, III
b) III, II, I
c) II, I, III
d) III, I, II
e) I, III, II
Answer: E
Section: 12.2
a) I, II, III
b) III, II, I
c) II, I, III
d) III, I, II
e) I, III, II
Answer: A
Section: 12.2
7
a) I, II, III
b) III, II, I
c) II, I, III
d) III, I, II
e) I, III, II
Answer: D
Section: 12.2

CH3CN H2NCH2CH2NH2 CH3CH2NH2
I II III
a) I, II, III
b) III, II, I
c) II, I, III
d) III, I, II
e) I, III, II
Answer: B
Section: 12.2

CH2Cl2 HCOOH CH3OH
I II III
a) I, II, III
b) III, II, I
8
c) II, I, III
d) III, I, II
e) I, III, II
Answer: D
Section: 12.2

CH3Cl CH3MgCl
a) reduction
b) oxidation
c) addition
d) elimination
e) rearrangement
Answer: A
Section: 12.2
a) Reduction
b) oxidation
c) Addition
d) elimination
e) Rearrangement
Answer: A
Section: 12.2
9
a) Reduction
b) oxidation
c) Addition
d) elimination
e) Rearrangement
Answer: A
Section: 12.2
23) List the following alkyl halides in order of increasing ease of Grignard formation:
RBr RCl RI RF
I II III IV
a) I, II, III, IV
b) III, I, II , IV
c) IV, II, I, III
d) III, I, IV, II
e) I, IV, III, II
Answer: B
Section: 12.2
24) Which product is formed from the following transformation:

O
1. LAH
O ?
2. H3O+
a)
O
OH
10
b)
HO
OH
c)
d)
H
HO
O
e)
O
OCH3
Answer: B
Topic: Synthetic Strategy, Redox

Section: 12.2
25) Which of these compounds will not be reduced by LiAlH4?
a) CH3CH2CH2CH=CH2
H
b) CH3CH2CH2C O
O
c) CH3CH2CH2COH
O
d) CH3CH2CH2COCH3
O
e) CH3CH2CH2CCH3
Answer: A

Section: 12.3
26) Which reagent(s) is/are capable of reducing the following ester to a primary alcohol?
11
O
O
a) LiAlH4 / ether
b) NaBH4 / H2O
c) Na / C2H5OH
d) H2 / Ni, atmospheric pressure
e) All can be used successfully.
Answer: A

Section: 12.3
27) Which of the reagents listed below would efficiently accomplish the transformation of 3-
methyl-3-cyclopentenone into 3-methyl-3-cyclopentenol?
O OH
?
a) i) LiAlH4; ii) H2O

b) NaBH4,H2O
c) H2, Pd
d) More than one of these choices.
Answer: D

Section: 12.3
28) Which of the reagents listed below would efficiently accomplish the transformation of ethyl-
3-pentenoate into 3-penten-1-ol?
O ? HO
a) i) LiAlH4; ii) H2O

b) NaBH4,H2O
c) H2, Pd
d) Two of these choices.
Answer: A
12
Section: 12.3
29) Which reagent(s) would you use to convert CH3(CH2)6CO2H to CH3(CH2)6CH2OH?
a) NaBH4/H2O
b) LiAlH4/ether, then H3O+
c) PCC/CH2Cl2
d) Zn, H3O+
e) H2, Pt
Answer: B

Section: 12.3
30) Which of these compounds cannot be reduced by sodium borohydride?
a) (CH3)2CHC O
O
b) CH3CH2CCH3
O
c) C6H5COH
O
d) CH3(CH2)4COCH3
e) Two of these choices cannot be reduced.
Answer: E

Section: 12.3
31) In the reaction of carbonyl compounds with LiAlH4, the effective reducing species is:
a) Li+
13
b) Al+3
c) AlH4-
d) AlH3
e) H-
Answer: E
Topic: Redox, Reaction Mechanisms

Section: 12.3
32) Which of the reagents listed below would efficiently accomplish the transformation of
CH3CH2CH=CHCH2CH2CHO into CH3CH2CH=CHCH2CH2CH2OH?
a) KMnO4
b) NaBH4
c) Br2 in CCl4
d) H2, Ni
e) Two of these choices.
Answer: B

Section: 12.3
CH3CH2CH=CHCH2CH2CH2OH into CH3CH2CH=CHCH2CH2CHO?
a) KMnO4(aq, alkaline)
b) CrO3 / H2SO4
c) PCC in CH2Cl2
d) Br2, CCl4
Answer: C

Section: 12.4
14
b) CrO3 / H2SO4
c) (i) (COCl)2, DMSO, -60oC, (ii) Et3N
d) Br2, CCl4
Answer: C

Section: 12.4
b) CrO3 / H2SO4
c) PCC in CH2Cl2
d) (i) (COCl)2, DMSO, -60oC, (ii) Et3N
Answer: E

Section: 12.4
CH3CH2C≡CCH2CH2CHO into CH3CH2C≡CCH2CH2CH2OH?
a) KMnO4
b) NaBH4
c) Br2 in CCl4
d) H2, Ni
Answer: B

Section: 12.3
15
CH3CH2CH=CHCH2CH2CHO into CH3CH2CH2CH2CH2CH2CH2OH?
a) KMnO4
b) NaBH4
c) Br2 in CCl4
d) H2, Ni
Answer: D

Section: 12.2
38) Select the correct reagent(s) for the following reaction:
O OH
CH3CCH2CH2CO2CH3 CH3CHCH2CH2CH2OH
a) LiAlH4/ether; then H3O+

b) NaBH4; then H3O+
c) H2 with Pt/C
Answer: A

Section: 12.3
39) Select the correct reagent(s) for the following reaction:
O OH
CH3CCH2CH2CO2CH3 CH3CHCH2CH2CO2CH3
a) LiAlH4/ether; then H3O+

b) NaBH4; then H3O+
c) H2 with Pt/C
16
Answer: D

Section: 12.3
40) Which of the reagents listed below would efficiently accomplish the transformation of 2-
methyl-3-cyclopentenol into 2-methyl-3-cyclopentenone?
OH O
?
b) CrO3/H2SO4
c) H2, Pt
d) Br2, CCl4
Answer: B

Section: 12.4
41) Which reagent(s) is/are capable of reducing the following ester to an aldehyde?
O
O
a) LiAlH4 / ether
b) NaBH4 / H2O
c) Na / C2H5OH
d) H2 / Ni, atmospheric pressure
e) None of these choices can be used successfully.
Answer: E

Section: 12.3
42) Which product is formed from the following transformation:
17
O
O 1. excess CH3MgBr
?
2. H3O+
a)
O
OH
b)
O OH
c)
HO
HO
d)
O
H OH
e) None of these choices.
Answer: C

Section: 12.8
C6H5
CH3CH2CH2CCH3
43) Your task is to synthesize OH through a Grignard synthesis. Which pairs of

compounds listed below would you choose as starting materials?
a) CH3CH2CH2Br and CH3CC6H5

O
b) CH3CH2CH2CH and C6H5Br

O CH3CH2CHCH3
and
c) C6H5CH Br
18
Answer: A
Topic: Synthetic Strategy

Section: 12.8
HO
44) Your task is to synthesize through a Grignard synthesis. Which pairs of

compounds listed below would you choose as starting materials?
O
Br
and
a)
Br
and
b)
O
Br
and
c)
O Br
and
d)
Answer: B

Section: 12.8
45) How could the following synthesis be accomplished?
19
O
OH CH2CH
a) (1) SOCl2, (2) Mg, ether, (3) CH3CH, then H3O+

b) (1) SOCl2, (2) Li, ether, (3) (CH3CH2)2CuLi, (4) KMnO4, OH-
O
c) 1) PBr3, (2) Mg, ether, (3) CH2 CH2, then H3O+ (4) PCC,CH2Cl2
Answer: C

Section: 12.8
Difficulty Level: Hard
46) Which of the following synthetic procedures would be employed most effectively to
transform ethanol into ethyl propyl ether?
a) Ethanol + HBr, then Mg/ether, then H3O+, then NaH, then CH3CH2Br
b) Ethanol + HBr, then Mg/ether, then HCHO, then H3O+, then NaH, then CH3CH2Br
c) Ethanol + CH3CH2CH2OH + H2SO4/140C
d) Ethanol + NaH, then HCHO, then H3O+, then HBr, then Mg/ether, then CH3CH2CH2Br
e) Ethanol + H2SO4/180°C, then CH3CH2CH2Br
Answer: B

Section: 12.8
47) Which reaction leads to an optically active product?
+ NaBH4
a) O
O
+ ClMg
b)
H CO2H
+ H2, Pt
c)
20
+ KMnO4
d) H OH
e)
H3C CHO
O LiAlH4/Et2O
+
excess
O
Answer: C
Topic: Synthetic Strategy, Stereochemistry

Section: 12.8
OH
48) Which method would give (CH3)2CC CH ?

CH3CHCH3 H2CrO4 HC CNa NH4+
acetic
OH
a) acid
CH3CCH3 CH3CH2Li H 3O+ H2CrO4
acetone
b) O
CH3CC CH 2 CH3MgBr NH4+
c) O
Answer: D

Section: 12.4 and 12.8
49) Which combination of reagents is to be preferred for the synthesis of 2,4-dimethylhexane by

the Corey-Posner, Whitesides-House procedure?
a) Lithium diisobutylcuprate + sec-butyl bromide

b) Lithium dimethylcuprate + 2-bromo-4-methylhexane
c) Lithium dimethylcuprate + 4-bromo-2-methylhexane
d) Lithium diisopropylcuprate + 1-bromo-2-methylbutane
21
e) Lithium di(2-methylbutyl)cuprate + isopropyl bromide
Answer: D

Section: 12.3
50) Which of these reduction reactions would be unsuccessful?
a) CH3CH2CH2COCH2CH2CH3 + LiAlH4, ether

H
b) C6H5CH2C O + NaBH4, CH3OH

O
c) CH3(CH2)10COH + H2, Pt, high pressure

O
d) C6H5CCH2CH2CH2CH3 + NaBH4, CH3CH2OH

e) All of these are successful reductions.
Answer: C

Section: 12.3
51) What would be the product, A, of the following reaction?
i) NaBD4
A
O ii) H2O
a) OD
D
b) OH
D
c) OD
d) OH
22
D
e) O
Answer: B
Topic: Reactions and Reaction Sequences (Redox)

Section: 12.3
52) What is the major product from the reaction of 2-hexanol with PCC in CH2Cl2?
a) CH3CO2H
b) CH3(CH2)3CO2H
O
c) CH3(CH2)3CCH3
d) CH3(CH2)4CO2H
Answer: C

Section: 12.4
53) What is the major product from the reaction of 2-hexanol with KMnO4?
a) CH3CO2H
b) CH3(CH2)3CO2H
O
c) CH3(CH2)3CCH3
d) CH3(CH2)4CO2H
Answer: C

Section: 12.4
54) What is the major product from the reaction of 2-hexanol with Na2Cr2O7/H+?
23
a) CH3CO2H
b) CH3(CH2)3CO2H
O
c) CH3(CH2)3CCH3
d) CH3(CH2)4CO2H
Answer: C

Section: 12.4
55) What is the major product from the reaction of 2-hexanol with H2CrO4?
a) CH3CO2H
b) CH3(CH2)3CO2H
O
c) CH3(CH2)3CCH3
d) CH3(CH2)4CO2H
Answer: C

Section: 12.4
56) What is the major product from the reaction of toluene with KMnO4?
a)
b)
c)
24
OH
HO
HO OH
d) OH
e)
Answer: B

Section: 12.4
57) What would be the product, O, of the following reaction sequence?
CH3CH2CHCH3 Mg D2O
N O
Br
ether
a) CH3CH2CH2CH3
CH3CH2CHCH3
b) D
CH3CH2CHCH3
c) OD
d) CH3CH2CH2CH2OD
e) CH3CH2CH2CH2D
Answer: B
Topic: Reactions and Reaction Sequences

Section: 12.7
58) What compound(s) result(s) from the reaction of CH3CH2CH2MgBr with

CH3CH2CH2CH2CO2H (1:1 mole ratio)?
(CH3CH2CH2)2CCH2CH2CH2CH3
a) OH
25
O
b) CH3CH2CH2CCH2CH2CH2CH3
O
c) CH3CH2CH2CH2COCH2CH2CH3
d) CH3CH2CH3 + CH3CH2CH2CH2CO2MgBr
O O
e) CH3CH2COCCH2CH2CH2CH3
Answer: D

Section: 12.7
59) What is the principal product(s) formed when 1 mol of methylmagnesium iodide reacts with
1 mol of p-hydroxyacetophenone?
O
CH3MgI
A
HO
O O
OMgI
IMgO
+ CH4 HO O
I II III
O O
O MgI IMgO
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: A
Topic: Reactions and Reaction Sequences (Grignard)

Section: 12.7
26
60) What is the principal product(s) formed when 1 mol of methylmagnesium iodide reacts with
1 mol of p-hydroxyacetophenone?
a) I
b) II
c) III
d) IV
e) V
Answer: A

Section: 12.7
61) What would be the product, A, of the following reaction sequence?
OH
PBr3 Mg D2 O
A
ether
a) CH3CH2CH2CH3
CH3CH2CHCH3
b) D
CH3CH2CHCH3
c) OD
d) CH3CH2CH2CH2OD
e) CH3CH2CH2CH2D
27
Answer: B

Section: 12.7
OH
SOCl2 Mg D2O
A
ether
a) CH3CH2CH2CH3
CH3CH2CHCH3
b) D
CH3CH2CHCH3
c) OD
d) CH3CH2CH2CH2OD
e) CH3CH2CH2CH2D
Answer: B

Section: 12.7
a) CH3CH2CH2CH3
CH3CH2CHCH3
b) D
CH3CH2CHCH3
c) OD
d) CH3CH2CH2CH2OD
e) CH3CH2CH2CH2D
Answer: B
28
Section: 12.7
64) What is (are) the principal product(s) formed when 1 mol of ethylmagnesium bromide reacts
with 1 mol of 3-(N-methylamino)cyclopentanone?
a) I
b) II
c) III
d) IV
e) V
Answer: A

Section: 12.7
65) Predict the product(s) of the following reaction:
29
O
1. LiAlH4
?
2. H3O+
H CH3
OH OH OH OH
H H CH3 CH3
CH3 CH3 H H
H CH3 H3C H H CH3 H3C H

IV
I II III
a) A mixture of I and II
b) A mixture of I and III
c) A mixture of II and III
d) A mixture of II and IV
e) A mixture of III and IV
Answer: B

Section: 12.3
66). Predict the product(s) of the following reaction:
a) I
b) II
c) III
d) IV
e) A mixture of two or more of these choices.
Answer: D
30
Section: 12.4
67) What product(s) is/are formed in the following reaction?

O LiAlD4 D2O
?
CH3CH2CH2COCH2CH3 ether
a) CH3CH2CH2CH2OD + CH3CH2OD
b) CH3CH2CH2CD2OD + CH3CH2OD
c) CH3CH2CH2CD2OH + CH3CH2OH
d) CH3CH2CH2CHDOD + CH3CH2OD
OD
e) CH3CH2CH2CDOCH2CH3
Answer: B

Section: 12.3

O
1. LiAlD4
H ?
2. H3O+
H CH3
OH OH OH OH
H H D D
D D H H
IV
I II III
Answer: B
31
Section: 12.3
69) When 1-pentanol is treated with alkaline potassium permanganate,
a) the color changes from orange to blue.

b) the color changes from purple to colorless.
c) the color changes from blue to red.
d) the color changes from orange to green.
e) the color changes from green to orange.
Answer: B
Topic: Reactions and Reaction Sequences (Chemical Tests)

Section: 12.4

O
1. NaBH4
?
2. H3O+
H CH3
OH OH OH OH
H H CH3 CH3
CH3 CH3 H H
III IV
I II
Answer: B

Section: 12.3
71) The final product, D, in the following reaction sequence,
32
CH2 CH2
CH3CHOH PBr3 Mg O H3O+

A B C D
ether
CH3 , would
be?
CH3CHOCH2CH2OH
a) CH3
CH3CHCH2CH2Br
b) CH3
CH3CHCH2CH2OH
c) CH3
CH3CHOCH2CH3
d) CH3
CH3CHCH2CH3
e) CH3
Answer: C

Section: 12.7
72) The final product, B, in the following reaction sequence,

OH
SOCl2 1. LAH
2. H3O+
,would be?
a)
b)
33
c)
d)
Cl
e)
Answer: C

Section: 12.7
73) The final product, B, in the following reaction sequence,
,would be?
Br
a)
b)
O
c)
d)
N
Answer: B

Section: 12.7
74) The final product, D, in the following reaction sequence
34
PBr3 Mg H3 O+
OH A B C D
ether O
,
would be:
OH
O
a)
b) Br
c) OH
OH
d)
OH
e)
Answer: C

Section: 12.7
75) What is the product, A, that would be obtained from the following reaction sequence?
35
O
CH3CH2MgBr CH3CH CHCH3 H3 O+

C CH A
CH3 CH3 CH3 CH3
C CCH2CH3 C CCH CHOCH2CH3 CH3CH2 C CCH CHOH
I II III
CH3 CH3 CH3
C CCH CHOH C C O CHCH2CH3
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: D

Section: 12.7
76) What is the principal product of the following reaction:

O
CH3CH CH2 + CH3CH2CH2CH2MgBr/ether; then H2O  ?
CH3CHCH2CH2CH2CH3
a) CH2OH
OH
b) CH3CHCH2CH2CH2CH2CH3
OH
c) CH3CHCH2OCH2CH2CH2CH3
CH3CHOCH2CH2CH2CH3
d) CH2OH
36
CH3CHCH2OCH2CH2CH2CH3
e) OCH2CH2CH2CH3
Answer: B

Section: 12.7
77) What would be the final product, A, in the following reaction sequence?
O
OH PBr3 Mg, Et2O H3O+
A
heat
OH
O OH
I II III
Br
O
OH
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: C

78) What would be the final product, A, in the following reaction sequence?
37
O
OH SOCl2 Mg, Et2O H3O+
A
heat
OH
O OH
I II III
Br
O
OH
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: C

79) What would be the final product, D, in the following reaction sequence?
OH PBr3 Mg H3O+
A B C D
Ph ether O
OH
Ph Ph OH Ph
I III OH
II
OH
O
Ph
OH
V
IV
a) I
b) II
c) III
d) IV
38
e) V
Answer: A

80) What would be the final product, D, in the following reaction sequence?
a) I
b) II
c) III
d) IV
e) V
Answer: A

39
OH PBr3 Li (CH3)2C=O NH4Cl
A
10oC
OH
OH
I II III
HO
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: D

Section: 12.8
OH PBr3 Mg
Li (CH3)2C=O NH4Cl
A
ether 10oC
OH
OH
I II III
HO
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: D
40
Section: 12.8
OH SOCl2
PBr 3 LiMg (CH3)2C=O NH4Cl
A
ether 10oC
OH
OH
I II III
HO
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: D

Section: 12.8
+
OH PBr3 Mg, Et2O (CH3)2C=O H3O
A
heat
OH
OH
I II III
HO
IV V
a) I
41
b) II
c) III
d) IV
e) V
Answer: C

Section: 12.8
Answer: B

Section: 12.8
86) Predict the product(s) of the following reaction sequence:
42
Br Mg 1. CH3CHO
?
H CH3 ether 2. H3O+
H OH H H H3 C H OH H3C H
CH3 H CH3 HO H H HO
I II III IV
Answer: A

Section: 12.8

O
Br Mg 1. H3C Ph
?
H CH3 ether 2. H3O +
H OH H Ph H3C Ph OH H3C H
CH3 Ph CH3 HO H H Ph
I II III IV
Answer: A

Section: 12.8
43
Answer: B

Section: 12.8
89) What is/are the principal product(s) formed when excess methylmagnesium iodide reacts
with p-hydroxyacetophenone?
O
1. excess CH3MgI
CH3MgI
2. H3O+ A
HO
O OH
O
OMgI
IMgO
+ CH4 HO O
I HO II III
II
O O
O MgI IMgO
IV V
a) I
b) II
c) III
d) IV
e) V
44
Answer: B


Br
Mg 1. CH3COCl
?
ether 2. H3O+
O O
OH
I II III
O
OH O
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: D

91) What product(s) is/are produced in the 1:1 reaction of sec-butylmagnesium bromide with
OH H
?
CH3CHCH2CH2C O
45
OH OMgBr
CH3CHCH2CH2CHCCH2CH3
a) CH3
OMgBr H
b) CH3CHCH2CH2C O + CH3CH2CH2CH3
OH OMgBr
c) CH3CHCH2CH2CHCH2CH(CH3)2
OMgBr H
d) CH3CHCH2CH2C O + (CH3)3CH
H
CH3CHCH2CH2C O
OCHCH2CH3
e) CH3
Answer: B

Section: 12.8
CH3MgBr H3O+
C CH A
O
C C
C CCH3 C C
OH
O
II III
I
C C C C O OH
OH
IV V
a) I
46
b) II
c) III
d) IV
e) V
Answer: C

CH3CH2MgBr H3O+
C CH A
C CCH2CH3 C C
C C
OH
O
II III
I
C C C C O
OCH3
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: C

47
NaNH2 H3O+
C CH A
O
C C
C CCH3 C C
OH
O
II III
I
C C C C O OH
OH
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: C

Section: 12.8
O
CH3CH2MgBr CH3CH CHCH3 H3 O+

C CH NaNH2 A
CH3 CH3 CH3 CH3
C CCH2CH3 C CCH CHOCH2CH3 CH3CH2 C CCH CHOH
I II III
CH3 CH3 CH3
C CCH CHOH C C O CHCH2CH3
IV V
a) I
48
b) II
c) III
d) IV
e) V
Answer: D

Section: 12.8
O
NaNH2 CH3I CH3Mg H3O+
HC CH A
OH
II OH III
I
OH
OH
V
IV
a) I
b) II
c) III
d) IV
e) V
Answer: B

Section: 12.8
97) What is the final product?
49
O
NaNH2 CH3CCH3 CH3I

CH3C CH ?
liq. NH3
HO
CH3CC CCH3
a) CH3
OCH3
CH3CC CCH3
b) CH3
OCH3
c) CH3C COCH2CHCH3
CH3
CH3CC CONa
d) CH3
Answer: B

Section: 12.8
50
O
(CH3)3CSi(CH3)2Cl 1. excess CH3MgI

?
imidazole 2. H3O+
HO
OH OH
OH
H3CO HO HO
III
I II
O
OH
H3CO H3CO
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: C

Section: 12.9
51
O
OCH3 (CH3)3CSi(CH3)2Cl 1. excess CH3MgI

?
imidazole 2. H3O+
HO
OH OCH3
OH
H3CO HO HO
III
I II
O
OH
OCH3
H3CO H3CO
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: C

Section: 12.9
100) What would be the product, D, of the following reaction sequence?

OH Br
PBr3 Li CuI
A B C D
ether
I II III
IV V
52
a) I
b) II
c) III
d) IV
e) V
Answer: A

101) What would be the product, C, of the following reaction sequence?

CH3
CH3
Li CuI CH3CHCH2CH2Br
CH3CCH2Br A B C
ether
CH3
a) 2,6-Dimethylheptane
b) 2,2-Dimethylpropane
c) 2-Methylpentane
d) 2,2,5-Trimethylhexane
e) 2,2,6-Trimethylheptane
Answer: E

PBr3 Li CuI Br
OH A B C D
ether
b) 2,2-Dimethylpropane
c) 2-Methylpentane
d) 2,2,5-Trimethylhexane
e) 2,2,6-Trimethylheptane
53
Answer: E


Br
PBr3 Li CuI
OH A B C D
ether
I II III
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: D

104) What would be the alkane C that is the product of the following reaction sequence?
CH3
CH3CHBr Li CuI CH3CHCH2Br

A B C
CH3 ether
54
CH3
CH3CHCHCH2CH3
a) CH3
CH3CH CHCH2CH3
b) CH3 CH3
CH3
CH3CHCH2CHCH3
c) CH3
CH3
CH3CH CCH3
d) CH3 CH3
CH3
e) CH3CH2CH2CH2CHCH3
Answer: C

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

Cl Br
Li, Et2O CuI H CH3
A
a) (R)-3-ethyl-5-methylheptane
b) (R,S)-3-ethyl-5-methylheptane
c) (S)-3-ethyl-5-methylheptane
d) (3R,5S)-5-ethyl-3-methylheptane
e) (3S,5R)-5-ethyl-3-methylheptane
Answer: C

55
106) The reaction of lithium di-sec-butylcuprate with isopentyl bromide yields:
b) 2,6-Dimethylheptane
c) 3,5-Dimethylheptane
d) 3,4-Dimethylheptane
e) 3,6-Dimethylheptane
Answer: A

107) The reaction of lithium diethylcuprate with 1-bromo-4,4-dimethylhexane yields:
b) 3,3-Dimethyloctane
c) 1-Ethyl-4,4-dimethylhexane
d) Di-4,4-dimethylhexylcuprate
Answer: B

O i) NaBH4
A
ii) ethylene oxide, HA
OH O HO O
O O OH
I II III
O
HO O OH
OH
IV V
a) I
b) II
c) III
56
d) IV
e) V
Answer: A

Section: 12.3
i) NaBH4
A
O ii) NaH, Et2O
iii)
O S O
OCH2CH3
a) CH3CH2OCH(CH3)CH2CH2CH2CH3
b) (CH3CH2O)2CHCHOHCH2CH2CH3
c) (CH3CH2)2CHOHCH2CH2CHOHCH3
d) CH3OCH(C2H5)CH2CH2CH2CH3
e) CH3CH2CH(OCH3)CH2CH2CHOHCH3
Answer: A
Topic: Reactions and Reaction Sequences (Redox, SN2)

Section: 12.4, 12.6, and 12.7
110) The final product, E, in the following reaction sequence is,

O
PBr3 Mg H3O+ PCC
OH A B C D E
ether CH2Cl2
OH
H
I OH II III
O O
OH
V
IV
a) I
57
b) II
c) III
d) IV
e) V
Answer: C

Section: 12.4, 12.6 and 12.7
a) I
b) II
c) III
d) IV
e) V
Answer: C

Section: 12.4, 12.6 and 12.7
58
a) I
b) II
c) III
d) IV
e) V
Answer: C

Section: 12.4, 12.6 and 12.7
a) I
b) II
c) III
d) IV
e) V
Answer: C

59
Section: 12.4, 12.6 and 12.7

O
SOCl2 2 equi. Li H3O+ 1. (COCl)2, DMSO,
OH A B C D E
-60oC
2. Et3N
OH H
I OH II III
O O
OH
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: C

Section: 12.4, 12.6 and 12.7

PBr3 Mg CH2O H3O+ 1. (COCl)2, DMSO,
OH A B C D E
ether -60oC
2. Et3N
OH
H
OH
I II III
O O
IV O V
a) I
b) II
60
c) III
d) IV
e) V
Answer: C

Section: 12.4, 12.6 and 12.7
a) I
b) II
c) III
d) IV
e) V
Answer: C

Section: 12.4, 12.6 and 12.7
61
a) I
b) II
c) III
d) IV
e) V
Answer: C

Section: 12.4, 12.6 and 12.7
a) I
b) II
c) III
d) IV
e) V
62
Answer: C

Section: 12.4, 12.6 and 12.7
119) What is the final product of the following reaction sequence?

O
Mg, Et2O i) H2CrO4
CH3I A
+
ii) H3O acetone
O OH
O
O
I II III
OH O
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: E

Section: 12.4, 12.6 and 12.7
63
PBr3 Mg CH2O H3O+ PCC
OH A B C D E
ether CH2Cl2
OH
H
OH
I II III
O
O
IV O V
a) I
b) II
c) III
d) IV
e) V
Answer: C

Section: 12.4, 12.6 and 12.7
121) The reagent PCC in dry methylene chloride is successful in the selective oxidation of
primary alcohols to aldehydes because:
a) PCC is a relatively weak oxidizing agent.

b) primary alcohols cannot oxidize any further.
c) hydration of the intermediate aldehyde is unable to take place in dry methylene chloride.
d) methylene chloride is a reducing agent.
Answer: C

Section: 12.4
122) The Swern oxidation is a method successful for the selective oxidation of primary alcohols
to aldehydes because:
a) oxally chloride is a weak oxidizing agent.
64
b) primary alcohols cannot oxidize any further.
c) hydration of the intermediate aldehyde is unable to take place under the conditions employed.
d) DMSO is a reducing agent.
Answer: C

Section: 12.4
123) Fundamentally, 2-methyl-2-pentanol does not undergo oxidation by H2CrO4 because:
a) the intermediate chromate ester is not formed.

b) the oxidant isn't in a sufficiently high oxidation state.
c) the alcohol undergoes dehydration.
d) the intermediate chromate ester cannot lose hydrogen.
e) Actually, this oxidation does occur.
Answer: D

Section: 12.4
124) CrO3 in H2SO4/H2O will fail to give a positive test with which of these compounds?
a) CH3CH2CH2CH2OH
CH3CHCH2CH3
b) OH
c) (CH3)3COH
H
d) CH3CH2CH2C O
e) More than one of these choices.
Answer: C
Topic: Functional Group Tests

Section: 12.4
125) Jones reagent will fail to give a positive test with?

65
a)
b)
c)
OH
d)
Answer: D

Section: 12.4
126) Which reagent(s) will distinguish between cyclopentanol and cyclopentane?
a) Br2/CCl4
b) KMnO4 (cold)
c) CrO3/aqueous H2SO4
d) NaOH (aq)
e) Two of these choices
Answer: C

Section: 12.4
127) Which reagent(s) will distinguish between 2-methylcyclopentanol and 1-

methylcyclopentanol?
a) Br2/CCl4
b) KMnO4
66
c) CrO3/aqueous H2SO4
d) NaOH (aq)
Answer: E

Section: 12.4
128) Which of the reagents listed below would serve as the basis for a simple chemical test to
distinguish between (CH3)3COH and (CH3)2CHCH2OH?
a) NaH
b) NaOH/H2O
c) Br2 in CCl4
d) Cold conc. H2SO4
e) CrO3 in H2SO4
Answer: E

Section: 12.4
distinguish between (CH3)3COH and (CH3)2CHCH2OH?
a) NaH
b) NaOH/H2O
c) Br2 in CCl4
d) Cold conc. H2SO4
e) Jones reagent
Answer: E

Section: 12.4
130) Which of the following reagents might serve as the basis for a simple chemical test that
would distinguish between CH3CH=CHCH3 and CH3CHOHCH2CH3?
67
a) CrO3 in H2SO4
b) KMnO4
c) Br2 in CCl4
Answer: D

Section: 12.4
distinguish between CH3CH=CHCH2OH and CH3CH2CH2CH2OH?
a) CrO3 in H2SO4
b) Cold conc. H2SO4
c) Br2 in CCl4
d) NaOH/H2O
e) NaBH4
Answer: C

Section: 12.4
distinguish between (CH3)2C=CHCH2CH2OH and (CH3)2CHCH2CH2CH2OH?
a) CrO3 in H2SO4
b) Cold conc. H2SO4
c) Br2 in CCl4
d) NaOH/H2O
e) NaBH4
Answer: C

Section: 12.4
68
CH3
133) Consider the molecule CH3CHC CHCH2OH.

Which reagent will not give a positive test with this compound?
a) Cold conc. H2SO4

b) Br2/CCl4
c) NaOH (aq)
d) CrO3/H2SO4
e) Dilute KMnO4/H2O
Answer: C

Section: 12.4
134) When 2-pentanol is treated with chromic acid,

c) the color changes from blue to red.
e) the color changes from green to orange.
Answer: D

Section: 12.4
135) When 3-methyl-3-pentanol is treated with chromic acid,

c) the purple color remains unchanged.
e) the orange color remains unchanged.
Answer: E

Section: 12.4
69
136) Which of the reagents/techniques listed below would serve as the basis for a simple
chemical test to distinguish between 2-methyl-3-hexyn-2-ol and 2-methyl-5-hexyn-1-ol?
a) CrO3 in H2SO4
b) IR spectroscopy
c) Br2 in CCl4
d) Both CrO3 in H2SO4 and IR spectroscopy.
Answer: D

chemical test to distinguish between 2-methyl-3-hexyn-1-ol and 2-methyl-5-hexyn-1-ol?
a) CrO3 in H2SO4
b) Cold conc. H2SO4
c) Br2 in CCl4
d) NaBH4
e) IR spectroscopy
Answer: E

chemical test to distinguish between CH3CH2CH=CHCH2CH2CHO and
CH3CH2CH=CHCH2CH2CH2OH?
a) KMnO4
b) IR spectroscopy
c) Br2 in CCl4
Answer: B
70
139) Which of these is the least reactive type of organometallic compound?
a) RK
b) R2Hg
c) RLi
d) R2Zn
e) R3Al
Answer: B
Topic: Reactivity of Grignards and Other Organometallics

Section: 12.5
140) If the role of the solvent is to assist in the preparation and stabilization of the Grignard
reagent by coordination with the magnesium, which of these solvents should be least effective?
CH3CH2OCH2CH3 (CH3CH2)3N
O
I II III
CH3(CH2)4CH3 CH3OCH2CH2OCH3
IV V
a) I
b) II
c) III
d) IV
e) V
Answer: D
Topic: Synthesis of Grignards and Other Organometallics

Section: 12.6
141) Grignard reagents react with oxirane (ethylene oxide) to form 1 alcohols but can be
prepared in tetrahydrofuran solvent. Why is this difference in behavior observed?
a) Steric hindrance in the case of tetrahydrofuran precludes reaction with the Grignard.
71
b) There is a better leaving group in the oxirane molecule.
c) The oxirane ring is the more highly strained.
d) It is easier to obtain tetrahydrofuran in anhydrous condition.
e) Oxirane is a cyclic ether, while tetrahydrofuran is a hydrocarbon.
Answer: C

Section: 12.7
142) Which synthesis of a Grignard reagent would fail to occur as written?
Mg, ether
a) CH3OCH2CH2Br CH3OCH2CH2MgBr
Mg, ether
b) CH3CH2CH2I CH3CH2CH2MgI
Mg, ether
c) HO 2CCH 2 CH 2I HO2CCH2CH2MgI
Mg, ether
d) C 6 H 5 Br C6H5MgBr
e) All of these choices will succeed.
Answer: C

Section: 12.8
143) Which of these reactions will not produce a 1 alcohol?
a)
1. LiAlH4/Et2O
(CH3)2CHCH2CH2CHO
2. H3O+
1. CH2 CH2
O
(CH3)2CHCH2CH2MgBr
b) 2. H3O+
O 1. NaBH4
c) C6H5CCH3 2. H3O+
72
1. H2C=O
CH3CH2CH2CH2Li
d) 2. H3O+
1. LiAlH4, Et2O
CH3(CH2)5COOH
e) 2. H3O+
Answer: C

144) Which of the following would serve as a synthesis of racemic 2-methyl-1-phenyl-2-

butanol?
MgBr
1. Et2O
+
I
O 2. NH4+
1. Et2O
II + CH3CH2MgBr
2. NH4+
1. Et2O
III + CH3MgBr
2. NH4+
a) I
b) II
c) III
d) All of these choices.
Answer: D

Section: 12.8
73
145) Which of the following reactions would serve as a reasonable synthesis of the following
racemic alcohol (2-phenyl-2-butanol)?
OH
CH3CC6H5
C2 H5
a)
O
1. Et2O
CH3CC6H5 + C2H5MgBr
2. NH4+
O 1. Et2O
+ CH3MgBr
C2H5CC6H5 2. NH4+
b)
O 1. Et2O
+ C6H5MgBr
2. NH4+
c) CH3CC2H5
Answer: E

Section: 12.8
146) Which Grignard synthesis will produce an optically active product or product mixture?
MgBr
+
a) O
O
+ ClMg
b)
O
O + MgI
c)
H CH3
O +
d) MgI
74
H3C H
+ MgBr
e) O
Answer: E

Section: 12.8
147) Which of the following is the strongest base?
a) RMgX
b) Mg(OH)X
c) RH
d) H2O
e) NaOH
Answer: A
Topic: Acid/Base
Section: 12.8
148) In which of the following series are the compounds arranged in order of decreasing
basicity?
a) CH3CH2MgBr > NaNH2 > HCCNa > NaOH > CH3CH2ONa

b) CH3CH2MgBr > NaNH2 > HCCNa > CH3CH2ONa > NaOH
c) HCCNa > CH3CH2MgBr > NaNH2 > CH3CH2ONa > NaOH
d) NaNH2 > CH3CH2MgBr > HCCNa > CH3CH2ONa > NaOH
Answer: B
Topic: Acid/Base
Section: 12.8
149) Which of these compounds cannot be used to prepare the corresponding Grignard reagent?
a) CH3OCH2CH2CH2Br
b) (CH3)3CCl
75
c) CH2=CHCH2Br
d) (CH3)2NCH2CH2Br
H
e) O CCH2CH2I
Answer: E

Section: 12.8
150) Which of these compounds can be used to prepare the corresponding Grignard reagent?
a) CH3CHOHCH2CH2CH2CH2Br
b) (CH3)3CHCHBrCH2CH2CO2H
c) BrCH=CHCH2CH2CH3
d) CH3NHCH2CH2Br
e) None of these choices can be used to prepare the corresponding Grignard reagent.
Answer: C

Section: 12.8
Question type: fill-in-the-blank
151) Because the carbonyl carbon bears a partial positive charge, it is susceptible to ___ attack.
Answer: nucleophilic
Topic: General
Section: 12.1
152) Because the carbonyl oxygen bears a partial negative charge, it is susceptible to ___ attack.
Answer: electrophilic
Topic: General
Section: 12.1
76
153) When nucleophilic addition to a carbonyl group occurs, the carbon attacked undergoes this
hybridization change:
Answer: sp2  sp3
Topic: General
Section: 12.1
154) A reaction which increases the hydrogen content or decreases the oxygen content of an
organic molecule is called a(n) ___.
Answer: reduction
Topic: General, Redox

Section: 12.2
155) A reaction which increases the oxygen content or decreases the hydrogen content of an
organic molecule is called a(n) ___.
Answer: oxidation

Section: 12.2
156) LAH is the abbreviation for the powerful reducing agent ___.
Answer: lithium aluminum hydride

Section: 12.3
157) A negatively charged hydrogen atom is called a ___.
Answer: hydride ion
77
Section: 12.3
158) In the reaction of carbonyl compounds with LiAlH4, the effective reducing species is:
Answer: H (hydride)
Topic: Redox Reactions

Section: 12.3
159) In the reaction of carbonyl compounds with NaBH4, the effective reducing species is:
Answer: H (hydride)

Section: 12.3
160) A solution of CrO3 or Na2Cr2O7 in aqueous sulfuric acid is called the ___.
Answer: Jones reagent
Topic: General, Redox Reagents

Section: 12.4
161) Upon reaction with a primary or secondary alcohol, the change in oxidation state of
chromium ion in Jones reagent is from ___ to ___.
Answer: CrVI to CrIII

Section: 12.4
162) Upon reaction with a primary or secondary alcohol with CrO3 in H2SO4, the alcohol is ___
and the CrO3 is ___.
Answer: oxidized; reduced
78
Section: 12.4
163) Upon oxidation of a 1 or 2alcohol with Jones reagent, the chromium ion goes from ___ to
___.
Answer: +6 to +3
Topic: General, Redox Reagents, Chemical Tests

Section: 12.4
164) The process of converting an alkyl halide to an alkane using LAH is a(n) ___ reaction.
Answer: reduction

Section: 12.5
165) Organomagnesium halides are known as ___.
Answer: Grignard reagents
Topic: General
Section: 12.6
166) Compounds that contain carbon-metal bonds are known as ___.
Answer: organometallic compounds
Topic: General
Section: 12.5
167) Key to the usefulness of PCC/CH2Cl2 as a selective oxidant for the production of aldehydes
from 1 alcohols is ___.
Answer: the inability to form a hydrate from the initially formed aldehyde [RCH(OH)2]
79
Section: 12.4
168) The selective oxidation of a primary alcohol to an aldehyde using oxalyl chloride, DMSO at
-60°C, followed by triethyl amine is referred to as the ___ oxidation.
Answer: Swern

Section: 12.4
169) Key to the usefulness of Swern oxidation as a selective oxidant for the production of
aldehydes from primary alcohols is ___.
Answer: the inability to form a hydrate from the initially formed aldehyde

Section: 12.4
Question type: Essay
170) PCC and CrO3 are both Cr(VI) reagents. However, PCC/CH2Cl2 is useful in oxidizing
primary alcohols to aldehydes, while the analogous reaction with CrO3/H2SO4 will typically
produce carboxylic acids. Why?
Answer: Both reagents first oxidize the alcohol to the corresponding aldehyde. Further oxidation
of aldehydes, to carboxylic acids, is facilitated in aqueous solutions, via formation of the
intermediate aldehyde hydrates (CrO3/H2SO4). When the solvent is non-aqueous, such as
CH2Cl2, these key intermediates cannot be formed, thereby preventing further oxidation of
aldehydes (with PCC/CH2Cl2).

Section: 12.4
Question type: Molecular Drawing
80
171) Draw the resonance structures that account for esters being less reactive toward NaBH4 than
aldehydes or ketones.
Answer:
O O
O
R' R'
R' R O R O
R O
Topic: Carbonyl Compounds Resonance Forms

Section: 12.1
172) What would be the major product, A, of the following reaction?

i) NaBH4
A
O ii) NaH, Et2O
iii) CF3
O S O
OCH2CH3
O
Answer:
Topic: Multistep Reactions

Section: 12.3
173) Predict the product of the following reaction:

O
NaBH4
O ?
Answer:
O
HO
81
Topic: Reactions, Selective Redox Reactions
Section: 12.3

O
1. NaBH4
?
2. H3O+
H CH3
Answer:
OH OH
H CH3
CH3 H
H CH3 and H CH3
Topic: Reactions, Redox

Section: 12.3

O
1. LiAlD4
H ?
2. H3O+
H CH3
Answer:
OH OH
H D
D H
H CH3 and H CH3
Topic: Reactions, Redox

Section: 12.3
176) For the ketone shown, indicate on the appropriate arrow which face is the re face, and
which face is si?
82
H3C
C O
H3CH2C
Answer:
re
H3C
C O
H3CH2C
si
Topic: Carbonyl Compounds, Prochirality, Stereochemistry

Section: 12.3
177) Which of the following molecules, if any, contains a prochrial carbon?

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

Section: 12.3
178) Which of the following molecules, if any, contains a prochrial carbon?
83
a) I
b) II
c) III
d) IV
Answer: C

Section: 12.3
179) For the ketone shown, indicate on the appropriate arrow which face is the re face, and
which face is si?
Ph
C O
H3CH2C
Answer:
si
Ph
C O
H3CH2C
re

Section: 12.3
180) For the aldehyde shown, indicate on the appropriate arrow which face is the re face, and
84
which face is si?
H
C O
H3C
Answer:
re
H
C O
H3C
si

Section: 12.3
181) For the aldehyde shown, indicate on the appropriate arrow which face is the re face, and
which face is si?
H3C
C O
H
Answer:
si
H3C
C O
H
re

Section: 12.3
85
182) Primary and secondary alcohols can be distinguished from most other compounds (with the
exception of aldehydes) because they will react rapidly with a solution of CrO3 in aqueous
sulfuric acid, causing a color change from ___ to ___.
Answer: orange; green

Section: 12.4
183) Diethyl ether, the most commonly used solvent for Grignard reactions, also acts as an
‘internal cooling agent’, preventing the overheating of the reaction mixture: what specific
property of diethyl ether is exploited here and why is it important to prevent the overheating of
the reaction mixture?
Answer: Diethyl ether is very volatile (35-36oc): its low boiling point ensures that reactions
carried out in diethyl ether solvent cannot become overheated (the maximum temperature cannot
exceed the b.p. of the solvent): this is important in Grignard reactions, because Grignard reagents
decompose at higher temperatures. Thus, the decomposition of the newly formed Grignard
reagent is minimized by use of this ‘internal cooling agent.’

Section: 12.6
184) Why can we not prepare a Grignard reagent from a molecule such as 4-bromo-1-butanol?
Answer: Because Grignard reagents are extremely strong bases and will react with the alcohol's
acidic proton to form the magnesium halide salt of the alcohol and R-H corresponding to the
organic group of the Grignard reagent used, i.e., undergoes an acid-base reaction.

Section: 12.8
86
185) The reactivity of organometallic compounds increases with the ___ of the carbon-metal
bond.
Answer: percent ionic character
Topic: Reactivity of Grignards and Other Organometallics

Section: 12.5
186) In a Grignard reagent, the carbon bonded to magnesium has a partial ___ charge and
therefore behaves as a(n) ___.
Answer: negative; nucleophile
Topic: Reactions of Grignards and Other Organometallics

Section: 12.7
187). A Grignard reagent will produce a primary alcohol when reacted with ___ and___.
Answer: formaldehyde; ethylene oxide

Section: 12.8
188) A Grignard reagent will produce a secondary alcohol when reacted with ___.
Answer: any aldehyde except formaldehyde

Section: 12.8
189) Reaction of an alkyllithium with a ketone produces, after acid work-up, a ___ alcohol.
Answer: Tertiary
87
Section: 12.8
190) Reaction of excess methyllithium with ethyl acetate (CH3CO2C2H5) produces, after acid
work-up, ___.
Answer: t-butyl alcohol: (CH3)3COH

Section: 12.8
191) Reaction of excess ethyl magnesium bromide with ethyl benzoate (C6H5CO2C2H5)
produces, after acid work-up, ___.
OH
Answer: 3-phenyl-3-pentanol:

Section: 12.8
192) Reaction of excess ethyl magnesium iodide with an ethyl acetate (CH3CO2C2H5) produces,
after acid work-up, ___.
Answer: 3-methyl-3-pentanol CH3CH2C(CH3)(OH)CH2CH3

Section: 12.8
193) NH4Cl is sometimes preferred instead of HCl or H2SO4 for “acid” work-up after Grignard
reactions, particularly when the expected and desired product is a tertiary alcohol: why?
Answer: NH4Cl provides mildly acidic conditions via partial hydrolysis of NH4Cl. Under
strongly acid conditions, a tertiary alcohol product can undergo facile dehydration to an alkene.
Topic: Grignard Reactions
88
Section: 12.8

O
1. PhMgBr
CH3 ?
+
2. H3O
H CH3
Answer:
OH OH
CH3 Ph
Ph CH3
H CH3 and H CH3
Topic: Reactions, Grignard

Section: 12.8

O
1. PhMgBr
H ?
+
2. H3O
H CH3
Answer:
OH OH
H Ph
Ph H
H CH3 and H CH3
Topic: Reactions, Grignard

Section: 12.8
196) Suggest a reasonable synthetic strategy for the synthesis of 3-ethyl-3-heptanol from
pentanoic acid, CH3CH2CH2CH2CO2H.
Answer: CH3CH2CH2CH2CO2H  i)SOCl2; ii) 2 equivalents CH3CH2MgBr (or CH3CH2Li); iii)

NH4Cl (H3O+)
89
O O
i) CH3CH2MgBr OH
SOCl2 (2 equivalents), Et2O
HO Cl
ii) NH4Cl
Topic: Multistep Synthetic Strategy

Section: 12.8
197) Suggest a reasonable synthetic strategy for the synthesis of 4-heptanol from 1-pentene.
Answer: 1-pentene  i)MCPBA; ii) CH3CH2MgBr (or CH3CH2Li); iii) NH4Cl (H3O+)
MCPBA O OH
i) CH3CH2MgBr, Et2O
ii) NH4Cl

Section: 12.7
198) Complete the following reaction sequence, giving structural details of all key intermediates.
4-methyl-1-hexene------------------
i) BH3, THF
ii) H2O2,NaOH
iii) SOCl2
iv) Mg, Et2O
iv) ethylene oxide
v) NH4Cl
Answer:
90
i) BH3,THF
HO
ii) H2O2, NaOH
SOCl2
Mg
ClMg Cl
Et2O
i) O
ii) NH4Cl
HO
Topic: Multistep Reaction Sequence

Section: 12.7
1-hexene------------------
i) HBr
ii) Li
iii) (CH3CH2)2C=O
iv) C2H5I
Br Li
HBr Li
O OLi
C2H5I
Answer:

Section: 12.8
1-hexene------------------
91
i) HBr/ROOR
ii) Li
iii) (CH3CH2)2C=O
iv) C2H5I
HBr Li Li
Br
ROOR
O OLi
C2H5I
Answer:

Section: 12.8
1. PBr3
OH 2. Mg/ether
O
3.
4. H3O+
Answer:
OH 1. PBr3 Mg MgBr
Br
ether
H3O+
BrMgO
BrMgO
OH OMgBr
92
Section: 12.8
202) Suggest a reasonable synthetic strategy for the synthesis of 3-methyl-3-hexanol from 3-
hexanol.
Answer: 3-hexanol- i) PCC or Swern ; ii) CH3MgBr (or CH3Li); iii) NH4Cl
OH O OH
PCC i) CH3MgBr, Et2O
CH2Cl2 ii) NH4Cl

203) Suggest a reasonable synthetic strategy for the synthesis of 2-methyl-3-hexanol from 1-
butanol.
Answer: 1-butanol  i) PCC or Swern; ii) (CH3)2CHMgBr (or (CH3)2CHLi); iii) NH4Cl (H3O+)
OH
PCC i) (CH3)2CHMgBr, Et2O
HO CH2Cl2 O ii) NH4Cl


Br Mg 1. CH3CHO
?
H CH3 ether 2. H3O+
Answer:
H OH H H
CH3 H
and CH3 HO
Topic: Multistep Reactions, Grignard

93
O
Br Mg 1. H3C Ph
?
H CH3 ether 2. H3O+
Answer:
H OH H Ph
CH3 Ph and CH3 HO


Br
Mg 1. CH3COCl
?
ether 2. H3O+
Answer:
OH


Br
O
Mg H3O+
ether
Answer:
94
HO


OH
O
PBr3 Mg H3O+
ether
Answer:
HO

209) Predict the major product(s) of the following reaction sequence:

OH
O
PBr3 Mg H3O+
ether heat
(-H2O)
Answer:

95
2-methyl-1-pentene------------------
i) BH3, THF
ii) H2O2,NaOH
iii) PCC, CH2Cl2
iv) CH3CH2C≡C:Na+
v) NH4Cl
i) BH3,THF
HO
ii) H2O2, NaOH
PCC,
CH2Cl2
i)  Na+
HO O
ii) NH4Cl
Answer:

Section: 12.8
2-methyl-1-pentene------------------
i) BH3, THF
ii) H2O2,NaOH
iii) (COCl)2, DMSO, -60°C
iv) Et3N
v) CH3CH2C≡C:Na+
vi) NH4Cl
96
Answer:

Section: 12.8
212) Suggest a reasonable synthetic strategy for the synthesis of 4-methyl-1,4-pentanediol from
methyl-4-hydroxybutanoate HOCH2CH2CH2COOCH3.
Answer:
O HO
1. TBSCl
HO HO
OCH3 2. excess CH3MgBr
3. H3O+
Topic: Multistep Synthetic Strategy (using protecting groups)

Section: 12.9
213) Suggest a reasonable synthetic strategy for the synthesis of 1,4-pentanediol from 4-
hydroxybutanal HOCH2CH2CH2CHO.
Answer:
O OH
1. TMSCl
HO HO
H 2. CH3MgBr
3. H3O+

Section: 12.9
97
214) Suggest a reasonable synthetic strategy for the synthesis of 4-methyl-1,4-pentanediol from
4-hydroxybutanone HOCH2CH2CH2COCH3.
Answer:
O HO
1. TMSCl
HO HO
2. CH3MgBr
3. H3O+

Section: 12.9
215) Predict the product D of the following reaction sequence:

PBr3 Li CuI Br
OH A B C D
ether
Answer:
Topic: Multistep Reactions

Section:12.6A and 12.8C
Bromocyclohexane------------------
i) Li
ii) CuI
iii) 4-methyl-1-bromohexane
Br Li
Li CuI CuLi
2
Br
Answer:
98
99

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What are some common reaction types discussed in the text?

What are some common reaction types discussed in the text?

What factors determine the level of oxidation of compounds?

What factors determine the level of oxidation of compounds?

Package title: Solomons Test Bank

Course Title: Solomons 11e

Question type: Multiple choice

Topic: General Carbonyl Information

a) sp2  sp3

Topic: General Carbonyl Information

3) The following transformation would be considered a(n)?

4) The following transformation would be considered a(n)?

5) The following transformation would be considered a(n)?

6) The following transformation would be considered a(n)?

7) The following transformation would be considered a(n)?

8) The following transformation would be considered a(n)?

9) Which reaction is an oxidation?

a) RCHO  RCO2H

10) Which of these transformations cannot be classified as a reduction?

a) RCH2Cl  RCH3

d) RCOR' RCH2OH + R'OH

11) List the following compounds in order of increasing level of oxidation:

12) List the following compounds in order of increasing level of oxidation:

14) List the following compounds in order of increasing level of oxidation:

15) List the following compounds in order of increasing level of oxidation:

16) List the following compounds in order of increasing level of oxidation:

17) List the following compounds in order of increasing level of oxidation:

18) List the following compounds in order of increasing level of oxidation:

19) List the following compounds in order of increasing level of oxidation:

20) The following transformation would be considered a(n)?

21) The following transformation would be considered a(n)?

22) The following transformation would be considered a(n)?

24) Which product is formed from the following transformation:

Topic: Synthetic Strategy, Redox

25) Which of these compounds will not be reduced by LiAlH4?

Topic: Synthetic Strategy, Redox

Topic: Synthetic Strategy, Redox

a) i) LiAlH4; ii) H2O

Topic: Synthetic Strategy, Redox

a) i) LiAlH4; ii) H2O

29) Which reagent(s) would you use to convert CH3(CH2)6CO2H to CH3(CH2)6CH2OH?

Topic: Synthetic Strategy, Redox

30) Which of these compounds cannot be reduced by sodium borohydride?

Topic: Synthetic Strategy, Redox

Topic: Redox, Reaction Mechanisms

Topic: Synthetic Strategy, Redox

Topic: Synthetic Strategy, Redox

Topic: Synthetic Strategy, Redox

Topic: Synthetic Strategy, Redox

Topic: Synthetic Strategy, Redox

Topic: Synthetic Strategy, Redox

38) Select the correct reagent(s) for the following reaction:

a) LiAlH4/ether; then H3O+

Topic: Synthetic Strategy, Redox

39) Select the correct reagent(s) for the following reaction:

a) LiAlH4/ether; then H3O+

Topic: Synthetic Strategy, Redox

Topic: Synthetic Strategy, Redox

Topic: Synthetic Strategy, Redox