Chapter 21 - Test Bank Chem 200

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

Chapter Number: 21
Question type: Multiple choice
1) The common name for 4-methylphenol is which of these?
a) Catechol
b) p-Cresol
c) Resorcinol
d) Hydroquinone
e) p-Xylenol
Answer: B
Topic: Nomenclature
Section: 21.1
Difficulty Level: Easy
2) Catecholamines contain in their structure:
a) A 1,3-benzenediol and an amino group
b) A p-cresol unit and an amino group
c) Hydroquinone unit and an amino group
d) A 1,2-benzenediol and an amino group
e) p-Xylenol unit and an amino group
Answer: D
Topic: Nomenclature
Section: 21.1
3) The common name for 3-methylphenol is which of these?
a) Catechol
b) m-Tolylol
c) m-Cresol
d) Hydroquinone
e) p-Xylenol
Answer: C
Topic: Nomenclature
Section: 21.1
4) A catechol is:
a) A 1,2-benzenediol
b) A 2-methylphenol
c) A 1,4-benzenediol
d) A 3-methylphenol
e) A 2-methylphenol
Answer: A
Topic: Nomenclature
Section: 21.1
5) The common name for 1,2-benzenediol is which of these?
a) Catechol
b) m-Cresol
c) Resorcinol
d) Hydroquinone
e) o-Xylenol
Answer: A
Topic: Nomenclature
Section: 21.1
6) What is the common name for:
OH
OH
a) m-Hydroxyphenol
b) m-Dihydroxybenzene
c) Resorcinol
d) 1,3-Dihydroxybenzene
e) 1,3-Benzenediol
2
Answer: C
Topic: Nomenclature
Section: 21.1
7) What is the IUPAC name for:
OH
a) p-Hydroxyphenol
b) p-Dihydroxybenzene
c) Resorcinol
d) 1,4-Dihydroxybenzene
e) 4-Methylphenol
Answer: E
Topic: Nomenclature
Section: 21.1
8) What is the IUPAC name for
OH
NO 2
a) m-Hydroxy-p-nitrotoluene
b) 3-Hydroxy-4-nitrotoluene
c) 5-Methyl-2-nitrophenol
d) 3-Methyl-2-nitrophenol
e) 2-Hydroxy-4methylnitrobenzene
Answer: C
Topic: Nomenclature
Section: 21.1
Difficulty Level: Medium
9) What is the IUPAC name for:
OH
Br
O
a) p-Hydroxy-m-bromoacetophenone
b) m-Bromo-p-hydroxypropiophenone
c) 3-Bromo-4-hydroxypropiophenone
d) 2-Bromo-4-propanoylphenol
e) 2-Hydroxy-5-propanoylbromobenzene
Answer: D
Topic: Nomenclature
Section: 21.1
10) Which of the following is 5-bromo-3-methyl-1-naphthol?
OH
OH
Br
OH
Br
Br
I
II
III
HO
OH
Br
IV
Br
V
a) I
b) II
c) III
d) IV
e) V
Answer: B
Topic: Nomenclature
Section: 21.1
11) The structure below is a blistering agent (vesicant) found in poison ivy,
This is a
a) cresol
b) resorcinol
c) hydroquinone
d) catechol
e) phenanthrol
Answer: D
Topic: Nomenclature
Section: 21.1, 21.2
12) Given the following phenols, which one is the most soluble in water?
a) I and IV
b) IV
c) III and IV
d) I, II and IV
e) I
Answer: B
Topic: Properties
Section: 21.3
13) The industrial synthesis of phenol from cumene hydroperoxide involves benzene, cumene
and a radical initiator. The mechanistic steps are:
a) Friedel-Crafts alkylation and rearrangement
b) Hydrolytic rearrangement and radical reaction

c) Friedel-Crafts alkylation and oxidation of cumene
d) Friedel-Crafts alkylation, cumene oxidation, hydrolytic rearrangement
e) Chain initiation, propagation, hydrolytic rearrangement
Answer: D
Topic: Industrial Synthesis
Section: 21.4
14) Identify the commercial preparation(s) of phenol.
a) Chlorobenzene
b) Benzene + O2
c) C6H5CH(CH3)2
d) Chlorobenzene
e) Chlorobenzene
+ NaOH at 350 C; then H3O+

+ O2; then H3O+, heat
+ NaOH at 350 C; then H3O+ and Benzene + O2
+ NaOH at 350 C; then H3O+ and C6H5CH(CH3)2 + O2; then H3O+, heat
Answer: E
Topic: Synthesis
Section: 21.4
15) What is the product of the following reaction.
a) I
b) IV
c) III
6
d) V
e) II
Answer: C
Topic: Synthesis
Section: 21.4
16) Which of the following phenols would have the largest pKa?
F
HO
O2 N
OH
CH 3
OH
II
III
OH
OH
Cl
IV
a) I
b) II
c) III
d) IV
e) V
Answer: C
Topic: Acid/Base
Section: 21.5
17) Which of the following phenols would have the smallest pKa?
NO2
HO
O
OH
OH
II
III
NH2
O
OH
HO
IV
a) I
b) II
c) III
d) IV
e) V
Answer: C
Topic: Acid/Base
Section: 21.5
18) Which of the following compounds would you expect to be the strongest acid?
a) CH3OH
b) C6H5CH2OH
c) p-CH3C6H4OH
d) C6H5OH
e) p-NO2C6H4OH
Answer: E
Topic: Acid/Base
Section: 21.5
19) Which compound would be most acidic?
a) Cyclohexanol
b) 1-Hexanol
c) Phenol
d) 4-Methylphenol
8
e) 4-Chlorophenol
Answer: E
Topic: Acid/Base
Section: 21.5
20) Which of the following would be the strongest acid?
HO
HO
CH 3
OH
II
III
OH
F3C
OH
Br
IV
a) I
b) II
c) III
d) IV
e) V
Answer: D
Topic: Acid/Base
Section: 21.5
21) Which of the following substances would have the smallest pKa?
NO 2
HO
O
OH
OH
II
III
NH2
OH
OH
HO
IV
a) I
b) II
c) III
d) IV
e) V
Answer: E
Topic: Acid/Base
Section: 21.5
22) Which of the following would be the strongest acid?
Br
OH
OH
OH
II
III
SO3H
OH
OH
HO
IV
a) I
b) II
c) III
d) IV
e) V
Answer: C
10
Topic: Acid/Base
Section: 21.5
23) Which of these species is the strongest base?
a) I
b) II
c) III
d) IV
e) V
Answer: B
Topic: Acid/Base
Section: 21.5
24) Order the following compounds in order of decreasing acidity.
a) IV > II > I > III > V

b) IV > II > III > V > I
c) IV > II > I > V > III
d) II > I > IV > III > V
e) IV > II > III > I > V
11
Answer: E
Topic: Reactions of Phenols as Acids
Section: 21.5
25) Match the following pKa i through v to the corresponding phenol a through e.
pKa Phenol
i 0.38 a 2,4-dinitrophenol
ii 3.96 b 4-chlorophenol
iii 9.20 c 2,4,6-trinitrophenol
iv 8.11 d 4-methylphenol
v 10.17 e 2-chlorophenol
a) i ____d____;
b) i ____c____;
c) i ____d____;
d) i ____a____;
e) i ____c____;
ii __e______;
ii __a______;
ii __a______;
ii __b__ _ __;
ii __b______;
iii ___b_____;
iii ___b_____;
iii ___b_____;
iii ___d_____;
iii ___a_____;
iv ___a_____;
iv ___e_____;
iv ___e_____;
iv ___e_____;
iv ___e_____;
Answer: B
Section: 21.5
Difficulty Level: Hard
26) Order the following compounds in order of decreasing acidity.
The decreasing acidity order is:

a) V > II > III > IV>I
b) V > I > III > II > IV
c) IV > III > II > V > I
12
v ___c_____
v ___d_____
v ___c_____
v ___c_____
v ___d_____
d) IV > II > III > I > V

e) II > IV > III > I > V
Answer: D
Section: 21.5
27) Which reagent will distinguish between C6H5OH and C6H5CH2OH?
a) NaHCO3 (aq)
b) NaOH (aq)
c) H2SO4
d) NaHCO3 (aq) and NaOH (aq)
e) NaOH (aq) and H2SO4
Answer: B
Topic: Acid/Base
Section: 21.5
28) Which reagent will distinguish between C6H5OCH3 and p-CH3C6H4OH?
a) NaOH (aq)
b) NaHCO3 (aq)
c) H2CrO4
d) NaOH (aq) and NaHCO3 (aq)
e) None of these choices.
Answer: A
Topic: Acid/Base
Section: 21.5
29) Which would be soluble in aqueous sodium bicarbonate?
a) Benzoic acid
b) 2-Chlorophenol
c) 2,4-Dinitrophenol
d) Compounds in more than one of these choices.
13
e) All of these choices.

Answer: D
Topic: Acid/Base
Section: 21.5
30) The following mixture is dissolved in diethyl ether and extracted with an aqueous solution of
NaHCO3. What compound(s) is(are) extracted in the aqueous phase?
a) III and IV
b) Only III
c) I, II, and III
d) Only I
e) I and III
Answer: B
Topic: Extraction
Section: 21.5
31) A mixture of phenol and benzoic acid is esterified with MeOH. How can you separate the
product of esterification?
a) Treat the mixture with aqueous NaOH and extract with ethyl ether. The product will be in the
ether.
b) Treat the mixture with aqueous NaOH and extract with ethyl ether. The product is retained in
the aqueous solution.
c) Treat the mixture with water and extract with ethyl ether. Only the product is extracted in
ether.
d) Add water to the reaction mixture the product will be dissolved in the water and the phenol is
extracted with ethyl ether.
e) The ester of the phenol is extracted with ethyl ether.
Answer: A
14
Topic: Extraction
Section: 21.5
NaOH. What compound(s) is(are) extracted in the aqueous phase?
a) III and IV
b) Only III
c) I, II, and III
d) Only I
e) I and III
Answer: E
Topic: Extraction
Section: 25.5
NaOH. What compound(s) is(are) retained in the diethyl ether phase?
a) III and IV
b) Only III
c) Only II
d) II and IV
e) I and III
Answer: D
Topic: Extraction
15
Section: 25.5
34) The factors increasing the acidity of phenols vs. alcohols are:
a) Electron withdrawing groups in the 4-position
b) Hybridization of carbon bearing the OH group and resonance stabilized cation formed by
ionization
c) Hybridization of carbon bearing the OH group, resonance forms of the neutral phenol and,
resonance stabilized conjugated base
d) Electron releasing substituents on the aromatic ring absent in aliphatic alcohols
e) Electron withdrawing groups in ortho position to the OH group and sp3 hybridized carbon
Answer: C
Topic: Reactions of Phenols as acids
Section: 21.5
35) Indicate the correct product, if any, of the following reaction.
HO
HBr
Br
Br
Br
Br
HO
HO
HO
Br
II
Br
III
Br
IV
a) I
b) II
c) III
d) IV
e) There is no net reaction.
Answer: E
Topic: Reaction Products
Section: 21.6
16
36) What are the products of the reaction of phenol with propanoic anhydride in the presence of
base?
a) I
b) II
c) III
d) IV
e) V
Answer: C
Section: 21.6
37) What is the product of the reaction of phenol and chloroacetic acid in basic solution,
followed by acidification?
17
O
O
Cl
OH O
OH
Cl
O
O
II
OH
III
OH
OH
O
O
IV
a) I
b) II
c) III
d) IV
e) V
Answer: D
Section: 21.6
38) Which method could be used for preparing methoxybenzene from phenol?
a) NaOH, then CH3I
b) NaOH, then CH3OSO3CH3
c) NaOH, then CH3OCH3
d) NaOH, then CH3I and NaOH, then CH3OSO3CH3
e) NaOH then CH3OH
Answer: D
Topic: Synthesis
Section: 21.6
39) Which of these is an acceptable synthesis of phenetole (ethyl phenyl ether)?
a)
18
Chlorobenzene
CH3CH 2ONa
100oC
Sodium phenoxide
CH3CH 2I
70oC
b)
Sodium phenoxide
(CH3CH2O)2SO2
c)
d)
100oC
CH 3CH2OH, H 2SO4
Phenol
70oC
e) More than one of these choices.

Answer: E
Topic: Synthesis
Section: 21.6
40) Refluxing anisole, CH3OC6H5, with excess concentrated HBr would yield which of these
product mixtures?
a) C6H5Br + CH3OH
b) C6H5OH + CH4
c) C6H5OH + CH3OH
d) C6H5Br + CH3Br
e) C6H5OH + CH3Br
Answer: E
Section: 21.7
41) Which products would be formed in the following reaction?
OCH 3
H 3C
conc. HBr (excess)

heat
a) Methoxybenzene + methyl bromide

19
b) 2-Methylphenol + methyl bromide

c) 2-Bromotoluene + methanol
d) 2-Bromotoluene + methyl bromide
e) Bromobenzene + methyl bromide
Answer: B
Section: 21.7
42) What are the products of the following reaction
a)
b)
c)
d)
e)
Answer: A
Topic: Cleavage of Alkyl Aryl Ethers
Section: 21.7
43) What would be the major product of the following reaction?
20
HO
Br2 (excess)
H 2O
?
Br
Br
HO
Br
HO
HO
HO
Br
II
Br
III
Br
IV
a) I
b) II
c) III
d) IV
e) A mixture of I and II
Answer: D
Section: 21.8
44) Which position is predicted to be the chief site of substitution when the following substance
reacts with bromine in carbon disulfide at 10C?
II
I
HO
III
IV
V
CH 3
a) I
b) II
c) III
d) IV
e) V
Answer: A
Topic: Relative Reactivities and General Considerations
Section: 21.8
45) Which one is more reactive toward electrophilic aromatic substitution, phenol or sodium
phenoxide?
21
a) Phenol is more reactive because the OH group activates the aromatic ring.
b) Phenoxide ion is more reactive because the RO- is better electron donor than OH.
c) Phenol is more reactive because resonance forms put a negative charge on the aromatic ring.
d) Phenoxide is more reactive because the sodium ion activates the aromatic ring.
e) Both are equally activated for electrophilic aromatic substitution.
Answer: B
Topic: Reactions of Benzene Ring of Phenols
Section: 21.8
46) What is the major product of the following reaction?
i) conc H2SO4,100oC
Phenol
ii) HNO3 / H2SO4, heat

iii) H3O+/H2O, heat, steam distill
a) p-Hydroxybenzenesulfonic acid
b) p-Nitrophenol
c) o-Nitrophenol
d) p-Nitrophenol and o-Nitrophenol
e) p-Hydroxybenzenesulfonic acid and p-Nitrophenol
Answer: D
Section: 21.8
47) What is the product of the following synthesis?
phenol
1. H 2SO4, 100oC
2. 2 equiv. Br2, H2O
3. dil. H 2SO4, heat
a) 2,3-Dibromophenol
b) 2,4-Dibromophenol
c) 2,6-Dibromophenol
d) 2-Hydroxy-3,5-dibromobenzenesulfonic acid
e) 2,4,6-Tribromophenol
22
Answer: C
Section: 21.8
48) What is the IUPAC name of the final product obtained via the following reaction sequence?
1. H2, Ni
2. NaNO2, HCl, 0-5oC
3. KI
4. Br2, 5oC, CS2
2-nitrophenol
a) 4-Bromo-2-iodophenol
b) 2-Bromo-4-iodophenol
c) 2,4-Dibromophenol
d) 2,4-Dibromo-6- iodophenol
e) 1-Bromo-3-iodobenzene
Answer: A
Section: 21.8
49) Which of the following reactions would yield p-tert-butylphenol?
a)
H3O +
Phenol +
b)
Phenol +
OH
H3O+
Cl
AlCl3
c)
Phenol +
d) All of these choices.

e) Two of these choices.
Answer: D
Topic: Synthesis
23
Section: 21.8
50) Which of these reactions does not produce phenol?
a)
O
i. NaOH, H2O
ii. H3O +
b)
H3O+
ONa
c)
O
HI
Cl
H 2O
100oC
d)
NH 2
e)
i. NaNO 2, H 2SO 4, H 2O, 0-5 oC

ii. Cu 2O, Cu 2+, H 2O
Answer: D
Topic: Synthesis
Section: 21.8
2-bromophenol
1. 2-bromopropane, AlCl3
2. NaOH
3. (CH3CO)2O
a) 1-Isopropyl-3-bromo-4-acetylbenzene
b) 2-Bromo-4-isopropyl -acetophenone
c) 3-Bromo-1-isopropyl-4-phenyl acetate
d) (2-Bromo-4-isopropyl)phenyl acetate
e) None of these choices correctly describes the product.
Answer: D
24
Section: 21.1, 21.6 and 21.8

52) What is the final product?
Phenol t-butyl chloride
AlCl3
i. NaOH
C10H14O
(para-isomer) ii. CH3CH2I
a) 1-tert-Butyl-4-ethoxybenzene
b) 1-tert-Butyl-4-ethylbenzene
c) 1-tert-Butoxy-4-ethoxybenzene
d) tert-Butyl ethyl ether
e) 1-tert-Butoxy-3-ethylbenzene
Answer: A
Section: 21.6 and 21.8
53) Which of the following would provide a synthesis of aspirin,
o-CH3COOC6H4COOH?
a) C6H5COOH, CH3COOH, AlCl3, heat; then H2O
b) CH3COOC6H5, CO2, heat; then H3O+
c) CH3COOC6H5, HCOOC2H5, C2H5O-; then H3O+; then HOd) C6H5OH, CO2, H3O+; separate isomers; then CH3COOH, AlCl3
e) C6H5OH, HO-, CO2, heat, pressure; then H3O+; then (CH3CO)2O
Answer: E
Topic: Synthesis
2-bromophenol 1. CH3I, base
2. Butanoyl chloride, AlCl3
3. Zn(Hg), HCl
4. conc HBr, heat
a) 1-Butanoyl-3-bromo-4-methoxybenzene
25
b) 2-Bromo-4-butylphenol
c) 3-Bromo-1-butyl-4-methoxybenzene
d) 3,4-Dibromo-1- butanoylbenzene
e) None of these choices correctly describes the product.
Answer: B
Section: 21.1, 21.6, 21.7 and 21.8
55) Which product is likely to be obtained during the following reaction of the isotope-labeled
allyl ether (14C-isotopic site marked with an asterisk)?
O
200oC
OH
OH
II
III
OH
OH
*
IV
a) I
b) II
c) III
d) IV
e) V
Answer: B
Section: 21.9
56) Predict the product of this Cope rearrangement:
26
C6H5
180oC
C6H 5
?
C6H5
C6H5
II
C 6H 5
III
C6H 5
IV
a) I
b) II
c) III
d) IV
e) V
Answer: C
Section: 21.9
57) What product is likely to be obtained by the action of Ag+ or Fe+3 on the following
substance?
OH
CH 3
Ag+ or Fe3+
OH
27
OH O
CH 3
OH
II
III
OH
CH 3
CH3
HO H
IV
a) I
b) II
c) III
d) IV
e) V
Answer: A
Section: 21.10
58) What is the product of the reaction of 1 mol of p-benzoquinone with 1 mol of isoprene (2methyl-1,3-butadiene)?
O
I
O
II
III
IV
a) I
b) II
c) III
d) IV
e) V
Answer: A
28

Section: 21.10
59) In terms of reactivity towards nucleophiles, bromobenzene is most similar to which of these?
a) Allyl bromide
b) Vinyl bromide
c) tert-Butyl bromide
d) Propyl bromide
e) Methyl bromide
Answer: B
Section: 21.11
60) What product(s) would you expect from the following reaction?
Br
O2N
NO2
i. NaOH, NaHCO3,
H2O, heat
ii. H3O+
Br
HO
NaO
NO2
O2N
O 2N
NO 2
II
HO
NH 2
III
a) I
b) II
c) III
d) Substantial amounts of I and II
e) Substantial amounts of I, II, and III
Answer: A
Section: 21.11
29
61) Which is the leaving group when the following substance reacts with sodium cyanide in
DMSO solution?
I
Br
VH
Br
II
III
NO 2
IV
a) I
b) II
c) III
d) IV
e) V
Answer: A
Section: 21.11
62) Which compound reacts most rapidly with CH3ONa?
Br
Br
Br
NO2
NO 2
II
III
NO 2
Br
Br
O2N
O2N
IV
NO2
a) I
b) II
c) III
d) IV
e) V
Answer: D
Topic: Nucleophilic Aromatic Substitution
30
Section: 21.11
63) Rank the following compounds according to their increasing rate of reaction toward
nucleophilic aromatic substitution (SNAr).
a) I < II < III < IV < V

b) II < III < V < I < IV
c) II < V < I < IV < III
d) II < I < V < IV < III
e) IV < III < I < V < I
Answer: C
Topic: Reactivity
Section: 21.11
64) What product is likely to be obtained when 1-bromo-2-nitrobenzene is heated with aqueous
NaHCO3?
a) 2-Bromophenol
b) 2-Nitrophenol
c) 2-Bromophenyl carbonate
d) 2-Nitrophenyl carbonate
e) Sodium 2-nitrophenoxide
Answer: E
Section: 21.11
65) What product is likely to be obtained when 1-chloro-3-nitrobenzene is heated with aqueous
NaHCO3?
31
a) 3-Chlorophenol
b) 3-Nitrophenol
c) 3-Chlorophenyl carbonate
d) Sodium 2-nitrophenoxide
e) None of these choices: no reaction is likely to occur
Answer: E
Section: 21.11
66) Which of these resonance structures makes the greatest contribution to the hybrid for the
intermediate in the SNAr reaction of o-chloronitrobenzene with methoxide ion?
a) I
b) II
c) III
d) IV
e) V
Answer: E
Section: 21.11
67) The formation of equal amounts of m-toluidine (m-aminotoluene) and p-toluidine in the
reaction of p-bromotoluene with sodium amide in liquid ammonia at -33 C suggests this species
as the reaction intermediate:
32
Br
NH 2
Br
NH 2
II
IV
III
a) I
b) II
c) III
d) IV
e) V
Answer: D
Section: 21.11
68) Aryl halides are specially unreactive due to:
a) Lack of resonance forms of the carbocation that would be formed in the SN1 mechanism
b) Blocked back-side attack, unstable phenyl cation for an SN1 mechanism and shorter and
stronger C-X bond
c) They does not allow back-side attack and the carbanion would be unstable
d) Sort and strong bonds of C-X despite the stable carbocation being form in the SN1 mechanism
e) Inability to form phenyl cation for an SN2 reaction and short and stron C-X bond.
Answer: B
Topic: Aryl-X and Nucleophilic Aromatic Substitutions (SNAr)
Section: 21.11
69) Which of the following would be most likely to undergo a nucleophilic substitution reaction
with aqueous sodium hydroxide by an addition-elimination mechanism?
33
Br
Br
Br
O
II
III
NO 2
Br
Br
NO2
NO 2
O2 N
IV
a) I
b) II
c) III
d) IV
e) V
Answer: D
Section: 21.11
70) What products would you expect from the following reaction?
4-Chlorotoluene
i. OH / H 2O, 400oC
ii. H3O+
a) 2-Methylphenol
b) 3-Methylphenol
c) 4-Methylphenol
d) 2-Methylphenol and 3-Methylphenol
e) 3-Methylphenol and 4-Methylphenol
Answer: E
Section: 21.11
71) What products(s) would you expect from the following reaction?
34
Cl
H 3C
NaNH 2
NH3(l), -33oC
NH2
H 3C
NH 2
H3C
H 3C
NH 2
III
II
a) I alone
b) II alone
c) III alone
d) Products I and II
e) Products I, II and III
Answer: D
Section: 21.11
72) What product should be obtained if benzyne is generated in the presence of 1,3-butadiene?
II
IV
III
a) I
b) II
c) III
d) IV
e) V
Answer: A
Section: 21.11
35

73) What product is likely to be obtained when 1-chloro-2-trifluoromethylbenzene is treated with
sodium amide in liquid ammonia?
a) 2-(Trifluoromethyl)aniline
b) 3-(Trifluoromethyl)aniline
c) 4-(Trifluoromethyl)aniline
d) 2-Chloroaniline
e) None of these choices: no reaction is likely to occur
Answer: B
Section: 21.11
74) Thymol, isolated from thyme, has the following structure:
OH
Which of the following types of signal is NOT expected to be observed in its 1H-NMR
spectrum?
a) Singlet
b) Doublet
c) Triplet
d) Septet
e) all of these types of signals are expected to be observed
Answer: C
Topic: Spectroscopic Analysis
Section: 21.12
75) Methyl salicylate, commonly found in topical muscle relaxants, has the following structure:
OH
O
O
36
Which of the following signals is NOT expected to be observed in its 1H-NMR spectrum?
a) Singlet at about 4 ppm (3H)
b) Quartet at about 7 ppm (4H)
c) Doublet at about 7 ppm (1H)
d) Singlet at about 6 ppm (1H)
e) Two of these types of signals are not expected to be observed
Answer: B
Section: 21.12
76) Eugenol, isolated from cloves, has the following structure:
OH
O
Which of the following signals is NOT expected to be observed in its 1H-NMR spectrum?
a) Singlet at about 4 ppm (3H)
b) Doublet at about 2.5 ppm (2H)
c) Singlet at about 7 ppm (1H)
d) Singlet at about 6 ppm (1H)
e) Triplet at about 3.5 ppm (3H)
Answer: E
Section: 21.12
77) Compound L has the molecular formula C11H16O. Compound L is insoluble in water but
dissolves in aqueous NaOH. The infrared spectrum of L shows a broad absorption band in the
3200-3600 cm-1 region; its 1H NMR spectrum consists of:
triplet,
singlet,
quartet,
singlet,
multiplet,
0.8 (3H)
1.2 (6H)
1.5 (2H)
4.5 (1H)
7.0 (4H)
37
The most likely structure for compound L is:
HO
HO
II
III
HO
IV
a) I
b) II
c) III
d) IV
e) V
Answer: E
Topic: Structure Identification
Question type: fill-in-the-blank
78) The commonly used name for hydroxybenzene is ___.
Answer: Phenol
Topic: Nomenclature
Section: 21.1
Question type: Essay
79) Draw the structure corresponding to the following IUPAC name:
4-benzyl-3,5-diiodophenol
38
Answer:
HO
Topic: Nomenclature
Section: 21.1
80) Give the IUPAC name of the following substance:
H 3C
H
O
O
HO
Answer: (R)-methyl 6-(4-hydroxyphenyl)-4-methylhexanoate

Topic: Nomenclature
Section: 21.1
81) Write the IUPAC name of aspirin and its use.
Answer: 2-Acetoxybenzoic acid used as pain reliever.
Topic: Nomenclature
Section: 21.1
(2E,4S)-4-(3-hydroxyphenyl)-2-pentenoic acid
H 3C
H
OH
O
Answer:
OH
Topic: Nomenclature
Section: 21.1
39

(R)-2-Bromo-5-(3-methylpentyl)phenol
H
CH3
Br
Answer:
OH
Topic: Nomenclature
Section: 21.1
84) Answer True or False
Because phenol contains a hydroxyl group, it is referred to as an alcohol, but the presence of the
benzene ring takes phenol out of the alcohol class. The reason is that phenol is remarkably stable
and is not able to react chemically as an alcohol.
Answer: False
Phenol earned a place in history as an antiseptic, but is commonly used today as an anesthetic.
Answer: False
When phenol dissolves in water, it functions as a weak acid.
Answer: True
Topic: General, physical properties of alcohols
Section: 21.3
85) What is the effect of electron releasing and withdrawing group on ring acidity?
Answer: Electron releasing group on phenol destabilizes the phenoxide ion and thus it becomes
less acidic. Electron withdrawing group on phenol stabilizes the phenoxide ion and thus it
becomes more acidic.
Topic: General, Acidity of phenols
Section: 21.3
86) What is the most important laboratory synthesis of phenols?
40
Answer: The most important laboratory synthesis of phenols is by hydrolysis of arenediazonium

salts.
Topic: Synthesis
Section: 21.4
87) Outline the steps involved in the synthesis of 3-bromo-4-methylphenol from 4-nitrotoluene.
Answer: i. Br2, FeBr3 ; ii) Fe, HCl; iii) NaNO2, H2SO4, 0-5oC; iv) Cu2O, Cu2+, H2O
Br
NO 2
OH
3-bromo-4-methylphenol
4-nitrotoluene
NO 2
Br2
FeBr3
Br
Br
NO 2
Fe
HCl
NH2
4-nitrotoluene
i. NaNO2, H2SO4
0-5oC
ii. Cu2O, Cu2+,
H2O
Br
OH
Topic: Synthesis
Section: 21.4
88) Outline the steps involved in the synthesis of 3-nitrophenol from 1,3-dinitrobenzene
Answer: i) NH3, H2S, EtOH; ii) NaNO2, H2SO4, 0-5oC; iii) Cu2O, Cu2+, H2O
41
O2N
O 2N
OH
NO 2
1,3-dinitrobenzene
O2N
NO2
NH3
H 2S
EtOH
O 2N
3-nitrophenol
i) NaNO2, H 2SO4, 0-5oC
NH 2
ii) Cu2O, Cu2+, H2O
O2N
OH
Topic: Synthesis
Section: 21.4
89) Outline the steps involved in the synthesis of 3-bromo-4-methylphenol from 4-nitrotoluene.
Answer: i. Br2, FeBr3 ; ii) Fe, HCl; iii) NaNO2, H2SO4, 0-5oC; iv) Cu2O, Cu2+, H2O
Br
NO 2
OH
4-nitrotoluene
NO 2
Br2
FeBr3
Br
Br
NO 2
Fe
HCl
NH2
4-nitrotoluene
i. NaNO2, H2SO4
0-5oC
ii. Cu2O, Cu2+,
H2O
Br
OH
Topic: Synthesis
Section: 21.4
90) Outline the steps involved in the synthesis of 3-nitrophenol from benzoic acid
42
Answer: i) HNO3, H2SO4 ; ii) SOCl2; iii) NH3; iv) Br2, NaOH; v) NaNO2, H2SO4,
0-5oC; vi) Cu2O, Cu2+, H2O
or
i) HNO3, H2SO4 ; ii) SOCl2; iii) NaN3; iv) heat; v) H2O; vi) NaNO2, H2SO4,
0-5oC; vii) Cu2O, Cu2+, H2O
O 2N
CO 2H
OH
3-nitrophenol
benzoic acid
O
OH
OH
HNO3
H2SO4
Cl
NH3
SOCl2
NO 2
NH2
NO2
NO2
Br2
NaOH
i) NaN3
ii) heat
iii) H2O
OH
NH 2
0-5oC
NO 2
i) NaNO2, H2SO4,
ii) Cu2O, Cu2+, H2O
NO2
3-nitrophenol
Topic: Synthesis, Hofmann/Curtius Rearrangement

Section: 21.4
91) The industrial synthesis of phenol from cumene involves the acid hydrolysis of the key
intermediate, cumene hydroperoxide (formed from cumene via oxidation). Outline the
mechanistic steps that lead to this oxidation product. Which other industrially important
substance is produced as a by-product in this reaction?
O OH
cumene hydroperoxide
H3O+
50-90oC
OH
phenol
Answer: This is a hydrolytic rearrangement reaction. Protonation of the OH group of cumene

hydroperoxide, leads to a 1,2-phenyl migration with concomitant loss of water. Nucleophilic
addition to the resultant carbocation ultimately leads to the formation of phenol. Another
43
industrially important substance, acetone, is formed as a by-product during this reaction, making
this a doubly attractive synthetic strategy.
O OH
H3O+
50-90oC
OH
OH
phenol
H3O+
O OH2
- H2O
+ O
acetone
acetone
- H3O+
HO
H2O
HO
phenol
H
O
H2O

Section: 21.4
92) Most of the worldwide industrial preparation of phenol is now based on the ___ (name
method).
Answer: cumene hydroperoxide method
Section: 21.4
93) The cumene hydroperoxide synthesis of phenol is industrially very satisfying, because it
takes two inexpensive starting materials, ___ and ___, and converts them into two valuable
products, phenol and ___.
Answer: benzene; propene; acetone
Section: 21.4
44
94) Propose three synthetic methods to outline the steps that could be used to carry out the
transformation shown below. Show all reagents and reaction conditions.
Answer:
Topic: Synthesis
Section: 21.4
95) A key step in the industrial synthesis of phenol from cumene is the oxidation of cumene to
cumene hydroperoxide with oxygen. Outline the mechanistic steps that lead to this oxidation
product.
O2
O OH
95-135oC
cumene
Answer: This is a radical chain reaction. A radical initiator is required to initiate the process,
which begins with abstraction of the benzylic hydrogen to produce a 3o radical. The ensuing
chain reaction leads to the formation of cumene hydroperoxide.
45
Initiation
Step 1
H
+ R.
. + R-H
cumene
Propagation
Step 2
+ . O-O .
O.
Step 3
O
. +
OH

Section: 21.4
96) Why is phenol more acidic than ethanol?
Answer: Due to formation of the phenoxide ion which is resonance stabilized. There is no such
stabilization in the ethoxide ion.
Topic: Acid/Base
Section: 21.5
97) Draw the structure of the ionic species obtained when the following substance is treated with
NaOH:
NH 2
OH
HO
NH 2
O- Na+
Answer: HO
Topic: Relative Acidity
46
Section: 21.5
98) Which is a stronger acid: phenol or p-cresol
Answer: Phenol is the stronger acid; p-cresol has higher pKa value than phenol because the
methyl group in p-cresol is an electron donating group, which donates electrons to the benzene
ring. Thus the O-H bond of cresol will be more tightly held in comparison to the O-H bond in
phenol.
Topic: Acid/Base
Section: 21.5
99) Arrange the following in increasing order of acidity (from least to most acidic).
Answer: IV < I < II < III

47
Topic: Acid/Base
Section: 21.5
100) For each of the following series of compounds, arrange the molecules in order of decreasing
acidity (most acidic to least acidic):
Answer: II<III<I
I<IV<III<II
IV<II<I<III
Topic: Acid/Base
Section: 21.5
101. Phenol is an enol. In water it will undergo an enol to keto tautomerization
1) Will this reaction likely go by a base or acid catalyzed mechanism? Show the mechanism.
2) Which is more stable the enol or ketoform? Why?
Answer: The keto enol tautomerization is a base catalyzed mechanism because the phenol is
acidic and easily deprotonated.
48
The enol form is more stable because it retains aromaticity.

Topic: Topic: Reaction Mechanisms
Section: 21.5
102) Suggest a simple chemical test to distinguish between 4-methylphenol and 2,4,6trinitrophenol, briefly explaining your rationale.
Answer: Both substances will dissolve in aq NaOH via an acid-base reaction. However, only
2,4,6-trinitrophenol, being significantly more strongly acidic, is likely to react with aq NaHCO3,
releasing gaseous CO2 (easily observed as effervescence). The differences in reactivity can be
attributed to the fact that nitro groups are strongly electron-withdrawing, while the methyl group
is weakly electron- donating.
NO 2
OH
OH
NO2
O 2N
stronger acid
gives CO2 with NaHCO3(aq)
weaker acid
no reaction with NaHCO3(aq)
Topic: Chemical Analysis, Relative Acidity

Section: 21.5
103) Draw the structure of the final product obtained when 2-nitrophenol reacts with acetic
anhydride in presence of base.
O
NO2
OH
Answer:
NO2
O
base
Topic: Reaction Product

Section: 21.6
49
104) Draw the structure of the final product obtained when 3-methylphenol is subjected to the
following reaction sequence:
i) NaOH; ii) CH3CH2CH2OSO2OCF3
Answer:
OH
i) NaOH
ii) CH3CH2CH2OSO2OCF3

Section: 21.6
105) Draw the structure of the final product obtained when 4-cyclopentylphenol is subjected to
the following reaction sequence:
NaOH; ii) CH3I; iii) NBS; iv) CH3ONa/CH3OH, heat
Answer:
OH
i) NaOH
ii) CH3I
iii) NBS
iv) CH3ONa, CH3OH, heat
Topic: Reaction Sequence

Section: 21.6
106) The insecticide Sevin is synthesized from 1-naphthol and methyl isocyanate (CH3-N=C=O).
Draw the structure of this insecticide.
Answer:
O
OH
O
+ CH3-N=C=O
Sevin
50
N
H
Topic: Synthesis
Section: 21.6
107) Suggest a reasonable synthetic strategy for the synthesis of 3-bromophenol from
acetophenone.
Answer: i) Br2, FeBr3; ii) MCPBA; iii) H3O+/heat
Br
OH
O
acetophenone
3-bromophenol
Br
Br
O
Br 2
FeBr3
MCPBA
acetophenone
H3O +
heat
Br
OH
3-bromophenol
Topic: Synthesis
Section: 21.6
108) Draw the major products formed by the reaction of phenol with each of the following:
(a)
(b)
(c)
(d)
(e)
(f)
HNO3 / H2SO4 / heat

CH3CH2Cl / AlCl3 / heat
H2SO4 / SO3/ heat
CH3CH2COCl / AlCl3 / heat, then /H2/Pd-C/ethanol
Na then add benzyl chloride
HBr
51
Answer:
Section: 21.6
109) Outline the steps involved in the synthesis of p-methoxybenzoic acid from phenol.
Answer: i) NaOH ; ii) CH3I; iii) Br2, FeBr3 ; iv) Mg, Et2O; v) CO2; vi) H3O+/heat
52
OH
p-methoxybenzoic acid
phenol
OH
OH
O
Br2
FeBr 3
i) NaOH
ii) CH 3I
Br
i) Mg, Et 2O
ii) CO2
iii) H 3O+
OH
(+ o-isomer)
Topic: Synthesis, Grignard Synthesis

Section: 21.6
110) Alcohols are converted to alkoxides with Na or NaH, while phenols are converted to
phenoxides with NaOH.
A milder base can be used with phenols because: ___.
Answer: Phenols are more acidic than water
Topic: Reactions
Section: 21.6
111) Complete the following Williamson synthesis
a = ____________ ;
b = __________
Answer: a = NaOH; b = X-(CH2)2CH3 with X =, Br, Cl, or I

Topic: Reactions
Section: 21.6
112) Outline the synthesis of 1,4-dimethoxybenzene from 1,4-dihydroquinone
53
Answer:
Topic: Reactions
Section: 21.6
113) In the following reaction draw the structure of the aromatic products I, II and III.
Answer:
Topic: Cleavage of Alkyl Aryl Ethers
Section: 21.7
114) Draw the cleavage mechanism of phenyl alkyl ether with HBr to give phenol and alkyl
bromide.
Answer:
Topic: Reaction Mechanisms
Section: 21.7
54
115) Draw the product(s) when:

(a) Phenol is heated with bromine in CS2
(b) Phenol is heated with bromine in water
Answer: (b)

Section: 21.8
116) Predict the product of each of the three reactions.
Answer:
55
Topic: Reactions Products

Section: 21.8
117) Consider the following synthesis and separation procedure:
What are compounds A and B?

A=
B=
What compound would distill? _____(A or b)

What compound would remain in the distillation flask?____(A or b)
Answer:
A=
B=
A because intramolecular hydrogen bonding reduced the boiling point.

B" because the intermolecular hydrogen bonding increases the boiling point.
Topic: Reactions of Benzene Ring of Phenols
Section: 21.8
118) When phenol is nitrated with dilute nitric acid, a mixture of o- and p- substituted products is
obtained. These products can then be separated by the technique of steam distillation. However,
analogous products from the nitration of methoxybenzene cannot be similarly separated by steam
distillation. Explain.
Answer: In order for efficient separation of substances (from a mixture) by steam distillation,
there must be relatively large differences in volatility. The more volatile substance passes over
with the steam, leaving the less volatile substance in the distillation flask.
Differences in the volatility of the o- and p- nitrophenols may be predicted by considering
hydrogen bonding effects: o-nitrophenol can exhibit intramolecular hydrogen bonding, while p56
nitrophenol can exhibit intermolecular hydrogen bonding. Consequently, o-nitrophenol is likely

to be significantly more volatile than p-nitrophenol, leading to the possibility of efficient
separation by steam distillation.
By contrast, since no hydrogen bonding is possible in the products obtained by nitration of
methoxybenzene, there is no predictable difference in volatility. Hence, these products cannot be
separated by steam distillation.
O
N
O
H
O
N
O
O
H
o-nitrophenol
intramolecular hydrogen bonding
more volatile
OCH 3
methoxybenzene
p-nitrophenol
intermolecular hydrogen bonding
less volatile
OCH 3
O2N
OCH3
NO 2
no hydrogen bonding in either product:

volatility dif f erences not likely to be signif icant
Topic: Synthesis, Separation of (o-, p-) Products

119) Discuss the following reactions:
(a) Williamsons synthesis
(b) Kolbes reaction
Answer: Williamsons synthesis
Kolbes reaction
57
The Kolbe reaction is better known as Kolbe-Schmitt reaction/Kolbe process. It is basically a

carboxylation reaction that benefits by heating sodium phenolate with carbon dioxide, under
pressure and then treating the result with sulphuric acid. The end result is a scented hydroxyl
acid also known as salicylic acid.
Topic: Synthesis
120) The Claisen and Cope rearrangements are two examples of a general class of reactions
called ___.
Answer: pericyclic reactions
Topic: Claisen, Cope Rearrangement
Section: 21.9
121) Name two pericyclic reactions. Are ions involved in the mechanism of reaction?
Answer: The Claisen and Cope rearrangement. There are not ions involved in the reaction
mechanism, there is only a concerted rearrangement of electrons.
Topic: Claisen, Cope Rearrangement
Section: 21.9
122) Draw the structure of the product obtained when the following substance is heated at hight
temperature:
O
Answer:
58
OH
heat
(Claisen R earrangement)

Section: 21.9
123) What is the product of the reaction:
b)
a)
c)
e)
d)
Answer: B
Topic: Claisen Rearrangement

Section: 21.9
OH
a)
b)
c)
59
d)
e)
Answer: C
Topic: Claisen Rearrangement
Section: 21.9
a)
b)
d)
e)
c)
Answer: A
Section: 21.10
60
126) Draw the structure of the product obtained when benzoquinone reacts with 2 molar
equivalents of 1,3-butadiene via a Diels Alder reaction.
Answer:
O
O
Diels Alder
Reaction
+
O
1 mol
O
2 mol

Section: 21.10
127) The carbon-halogen bonds in aryl and vinyl halides are both ___ (strength) and ___ (length)
than the corresponding bonds in alkyl halides.
Answer: shorter; stronger
Topic: General
Section: 21.11
128) Benzyne is a very unstable intermediate, because ___.
Answer: the two carbons involved in the extra bond are sp hybridized, causing a severe amount
of bond angle distortion and strain
Topic: Benzyne Intermediate
Section: 21.11
129) Write the structural formula of the major product(s) of reaction 1 to 6.
1.
Na
OH
2.
OH
CH3 C O C CH3
O
conc HI
O
CH3
reflux
61
3.
NaOH
4.
Cl
5.
Cl
350
O
N
N
O
NaOH, H2O
35
N
O
6.
Br
NaOH
OH
Answer:
Section: 21.6, 21.7 and 21.11
130) Nucleophilic aromatic substitution reactions (SNAr) take place via a delocalized carbanion
intermediate called a ___.
Answer: Meisenheimer complex
Topic: General, Nucleophilic Aromatic Substitution
Section: 21.11
62
131) Nucleophilic aromatic substitution reactions (SNAr) require three components: a good
leaving group on the aromatic ring, a strong nucleophile, and ___.
Answer: an electron-withdrawing substituent ortho or para to the leaving group
Section: 21.11
132) Draw the structure of the final product obtained when 1-chloro-2,4-dinitrobenzene is heated
with aqueous NaHCO3 at 100 oC, followed by neutralization with H3O+ .
NO2
NO 2
Cl
Answer:
O 2N
i. NaHCO 3 (aq), 100

ii. H 3O+
OH
oC
O2N

Section: 21.11
133) In general, there are two types of nucleophilic aromatic substitution mechanisms. These are:
___.
Answer: addition-elimination or SNAr; elimination-addition or benzyne
Section: 21.11
134) Draw the structure of the product likely to be obtained from the reaction between
acetoacetic ester, bromobenzene and 2 molar equivalents of sodium amide in liquid ammonia.
Briefly explain your rationale.
Answer: This is likely to be a benzyne mediated nucleophilic substitution reaction of
bromobenzene (elimination-addition mechanism). The first equivalent of sodium amide is likely
to promote elimination to form benzyne, while the 2nd equivalent of base would generate the
anion of acetoacetic ester, which can then react with the benzyne to give the following product:
63
O
O
Topic: Synthesis
Section: 21.11
64

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Chapter 21 - Test Bank Chem 200

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Package Title: Solomons Test Bank

Course Title: Solomons 11e

b) Hydrolytic rearrangement and radical reaction

+ NaOH at 350 C; then H3O+

a) IV > II > I > III > V

The decreasing acidity order is:

d) IV > II > III > I > V

e) All of these choices.

e) More than one of these choices.

conc. HBr (excess)

a) Methoxybenzene + methyl bromide

b) 2-Methylphenol + methyl bromide

ii) HNO3 / H2SO4, heat

d) All of these choices.

i. NaNO 2, H 2SO 4, H 2O, 0-5 oC

Section: 21.1, 21.6 and 21.8

Topic: Reaction Products

a) I < II < III < IV < V

Difficulty Level: Medium

The most likely structure for compound L is:

Answer: (R)-methyl 6-(4-hydroxyphenyl)-4-methylhexanoate

83) Draw the structure corresponding to the following IUPAC name:

Answer: The most important laboratory synthesis of phenols is by hydrolysis of arenediazonium

Topic: Synthesis, Hofmann/Curtius Rearrangement

Answer: This is a hydrolytic rearrangement reaction. Protonation of the OH group of cumene

Topic: Industrial Synthesis

Topic: Industrial Synthesis

Answer: IV < I < II < III

The enol form is more stable because it retains aromaticity.

Topic: Chemical Analysis, Relative Acidity

Topic: Reaction Product

Topic: Reaction Product

Topic: Reaction Sequence

HNO3 / H2SO4 / heat

Topic: Synthesis, Grignard Synthesis

Answer: a = NaOH; b = X-(CH2)2CH3 with X =, Br, Cl, or I

115) Draw the product(s) when:

Topic: Reaction Products

Topic: Reactions Products

What are compounds A and B?

What compound would distill? _____(A or b)

A because intramolecular hydrogen bonding reduced the boiling point.

nitrophenol can exhibit intermolecular hydrogen bonding. Consequently, o-nitrophenol is likely

no hydrogen bonding in either product:

Topic: Synthesis, Separation of (o-, p-) Products

(b) Kolbes reaction

Answer: Williamsons synthesis

The Kolbe reaction is better known as Kolbe-Schmitt reaction/Kolbe process. It is basically a

Topic: Reaction Product

Topic: Claisen Rearrangement

Topic: Reaction Product

i. NaHCO 3 (aq), 100

Topic: Reaction Product

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