Documente Academic
Documente Profesional
Documente Cultură
Topic: Nomenclature
Section: 21.1
Difficulty Level: Easy
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
Difficulty Level: Easy
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
Difficulty Level: Easy
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
Difficulty Level: Easy
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
Difficulty Level: Easy
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
Difficulty Level: Medium
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
Difficulty Level: Medium
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
Difficulty Level: Easy
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
Difficulty Level: Medium
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
Answer: E
Topic: Synthesis
Section: 21.4
Difficulty Level: Easy
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
Difficulty Level: Medium
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
Difficulty Level: Easy
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
Difficulty Level: Easy
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
Difficulty Level: Easy
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
Difficulty Level: Easy
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
Difficulty Level: Easy
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
Difficulty Level: Medium
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
Difficulty Level: Medium
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
Difficulty Level: Medium
24) Order the following compounds in order of decreasing acidity.
Answer: E
Topic: Reactions of Phenols as Acids
Section: 21.5
Difficulty Level: Medium
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
Topic: Reactions of Phenols as Acids
Section: 21.5
Difficulty Level: Hard
26) Order the following compounds in order of decreasing acidity.
12
v ___c_____
v ___d_____
v ___c_____
v ___c_____
v ___d_____
13
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
Difficulty Level: Medium
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
Difficulty Level: Medium
32) The following mixture is dissolved in diethyl ether and extracted with an aqueous solution of
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
Difficulty Level: Medium
33) The following mixture is dissolved in diethyl ether and extracted with an aqueous solution of
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
Difficulty Level: Medium
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
Difficulty Level: Medium
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
Difficulty Level: Easy
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
Topic: Reaction Products
Section: 21.6
Difficulty Level: Easy
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
Topic: Reaction Products
Section: 21.6
Difficulty Level: Medium
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
Difficulty Level: Medium
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
a)
b)
c)
d)
e)
Answer: A
Topic: Cleavage of Alkyl Aryl Ethers
Section: 21.7
Difficulty Level: Medium
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
Topic: Reaction Products
Section: 21.8
Difficulty Level: Easy
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
Difficulty Level: Easy
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
Difficulty Level: Medium
46) What is the major product of the following reaction?
i) conc H2SO4,100oC
Phenol
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
Topic: Reaction Products
Section: 21.8
Difficulty Level: Medium
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
Topic: Reaction Products
Section: 21.8
Difficulty Level: Medium
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
Topic: Reaction Products
Section: 21.8
Difficulty Level: Medium
49) Which of the following reactions would yield p-tert-butylphenol?
a)
H3O +
Phenol +
b)
Phenol +
OH
H3O+
Cl
AlCl3
c)
Phenol +
Section: 21.8
Difficulty Level: Medium
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)
Answer: D
Topic: Synthesis
Section: 21.8
Difficulty Level: Medium
51) What is the IUPAC name of the final product obtained via the following reaction sequence?
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
Topic: Reaction Products
24
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
Topic: Reaction Products
Section: 21.6 and 21.8
Difficulty Level: Medium
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
Section: 21.6 and 21.8
Difficulty Level: Medium
54) What is the IUPAC name of the final product obtained via the following reaction sequence?
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
Topic: Reaction Products
Section: 21.1, 21.6, 21.7 and 21.8
Difficulty Level: Medium
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
Topic: Reaction Products
Section: 21.9
Difficulty Level: Easy
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
Topic: Reaction Products
Section: 21.9
Difficulty Level: Medium
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
Topic: Reaction Products
Section: 21.10
Difficulty Level: Medium
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
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
Topic: Reaction Products
Section: 21.11
Difficulty Level: Easy
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
Topic: Relative Reactivities and General Considerations
Section: 21.11
Difficulty Level: Easy
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
Difficulty Level: Easy
63) Rank the following compounds according to their increasing rate of reaction toward
nucleophilic aromatic substitution (SNAr).
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
Topic: Reaction Products
Section: 21.11
Difficulty Level: Medium
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
Topic: Relative Reactivities and General Considerations
Section: 21.11
Difficulty Level: Medium
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
Topic: Relative Reactivities and General Considerations
Section: 21.11
Difficulty Level: Easy
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
Difficulty Level: Easy
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
Topic: Relative Reactivities and General Considerations
Section: 21.11
Difficulty Level: Easy
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
Topic: Reaction Products
Section: 21.11
Difficulty Level: Medium
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
Topic: Reaction Products
Section: 21.11
Difficulty Level: Medium
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
Topic: Reaction Products
Section: 21.11
35
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
Difficulty Level: Medium
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
Topic: Spectroscopic Analysis
Section: 21.12
Difficulty Level: Medium
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
Topic: Spectroscopic Analysis
Section: 21.12
Difficulty Level: Medium
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
HO
HO
II
III
HO
IV
a) I
b) II
c) III
d) IV
e) V
Answer: E
Topic: Structure Identification
Section: 21.5 and 21.12
Difficulty Level: Hard
Question type: fill-in-the-blank
78) The commonly used name for hydroxybenzene is ___.
Answer: Phenol
Topic: Nomenclature
Section: 21.1
Difficulty Level: Easy
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
Difficulty Level: Medium
80) Give the IUPAC name of the following substance:
H 3C
H
O
O
HO
H
OH
O
Answer:
OH
Topic: Nomenclature
Section: 21.1
Difficulty Level: Hard
39
CH3
Br
Answer:
OH
Topic: Nomenclature
Section: 21.1
Difficulty Level: Hard
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
Difficulty Level: Easy
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
Difficulty Level: Easy
86) What is the most important laboratory synthesis of phenols?
40
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
3-bromo-4-methylphenol
Topic: Synthesis
Section: 21.4
Difficulty Level: Hard
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
Difficulty Level: Hard
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
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
3-bromo-4-methylphenol
Topic: Synthesis
Section: 21.4
Difficulty Level: Hard
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
cumene hydroperoxide
H3O+
50-90oC
OH
phenol
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
cumene hydroperoxide
OH
phenol
H3O+
O OH2
- H2O
+ O
acetone
cumene hydroperoxide
acetone
- H3O+
HO
H2O
HO
phenol
H
O
H2O
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
Difficulty Level: Medium
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 hydroperoxide
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
cumene hydroperoxide
OH
HO
NH 2
O- Na+
Answer: HO
Topic: Relative Acidity
46
Section: 21.5
Difficulty Level: Easy
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
Difficulty Level: Easy
99) Arrange the following in increasing order of acidity (from least to most acidic).
Topic: Acid/Base
Section: 21.5
Difficulty Level: Easy
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
Difficulty Level: Medium
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
OH
NO2
O 2N
stronger acid
gives CO2 with NaHCO3(aq)
weaker acid
no reaction with NaHCO3(aq)
NO2
OH
Answer:
NO2
O
base
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
i) NaOH
ii) CH3I
iii) NBS
iv) CH3ONa, CH3OH, heat
O
+ CH3-N=C=O
Sevin
50
N
H
Topic: Synthesis
Section: 21.6
Difficulty Level: Medium
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
Difficulty Level: Medium
108) Draw the major products formed by the reaction of phenol with each of the following:
(a)
(b)
(c)
(d)
(e)
(f)
51
Answer:
Topic: Reaction Products
Section: 21.6
Difficulty Level: Medium
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)
a = ____________ ;
b = __________
53
Answer:
Topic: Reactions
Section: 21.6
Difficulty Level: Hard
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
Difficulty Level: Hard
114) Draw the cleavage mechanism of phenyl alkyl ether with HBr to give phenol and alkyl
bromide.
Answer:
Topic: Reaction Mechanisms
Section: 21.7
Difficulty Level: Medium
54
Answer:
55
B=
B=
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
Kolbes reaction
57
Topic: Synthesis
Section: 21.6 and 21.8
Difficulty Level: Easy
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
Difficulty Level: Easy
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
Difficulty Level: Easy
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)
b)
a)
c)
e)
d)
Answer: B
OH
a)
b)
c)
59
d)
e)
Answer: C
Topic: Claisen Rearrangement
Section: 21.9
Difficulty Level: Medium
125) What is the product of the reaction:
a)
b)
d)
e)
c)
Answer: A
Topic: Reaction Product
Section: 21.10
Difficulty Level: Easy
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
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:
Topic: Reaction Product
Section: 21.6, 21.7 and 21.11
Difficulty Level: Medium
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
Difficulty Level: Easy
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
Topic: General, Nucleophilic Aromatic Substitution
Section: 21.11
Difficulty Level: Easy
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
OH
oC
O2N
63
O
O
Topic: Synthesis
Section: 21.11
Difficulty Level: Medium
64