Chemistry 234

Chapter 16 Problem Set

Electrophilic Aromatic Substitution

1) Predict the product and draw the mechanism for electrophile generation for each of the
following reactions.

Cl2
(a)
FeCl3

HNO3
(b)
H2SO4

SO3
(c)
H2SO4

2) Explain why reaction of benzene with Br2/FeBr3 results in the product bromobenzne
instead of 5,6-dibromo-1,3-cyclohexadiene.

3) Predict the product and draw the active electrophile for each reaction shown below.

Cl
(a)
AlCl3

Cl
(b)
AlCl3

Cl

O
(c)
AlCl3

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 Chem. 234 – Chapter 16 Problem Set

4) Explain why each of the following substrates do not undergo Freidel-Crafts reactions.
NH2 NO2 N(CH3)3 NH

5) Arrange the following benzene substituents in order of reactivity in electrophilic aromatic

substitution reactions.
O
Cl
Ph Ph N
Ph Ph

H O
N H S
Ph N Ph
Ph Ph O
O

6) Predict the major products when the following benzene derivatives are treated to
nitration conditions (HNO3/H2SO4).
a.
O

Br

b. NH2
Br

c. NO2
Cl

7) Write the full electron pushing mechanism for the nitration of toluene.

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 Chem. 234 – Chapter 16 Problem Set
8) Predict the product(s) when each of the following benzene derivatives is treated to
chloroethane and AlCl3.

a. Br

b. NH2

Cl

c. OH

Br

d. OH
Cl

Cl

e. NO2
Cl

Cl

f.
Br

Br

g. SO3H

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 Chem. 234 – Chapter 16 Problem Set
9) Predict the product(s) when the following benzene derivatives are subjected to
electrophilic chlorination conditions (Cl2, FeCl3).

a. NO2

O OH

b. OH

NO2

c.

d. SO3H

Br

10)Predict the product(s) for each of the following reactions.

a. O Br O
Cl2
H3CO OCH3
FeCl3

b.
HNO3

H2SO4
OCH3

c.
SO3

H2SO4

d. HO SO3

H2SO4
Br NO2

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 Chem. 234 – Chapter 16 Problem Set

11)Predict the product for each benzene side-chain modification reaction shown below.
a.
KMnO4

b.
H2CrO4

c. NBS
light

d. NO2 H2
Pd/C

e. NO2 Sn
HCl

f. O
Zn(Hg)
HCl

g. O
N 2H 2
HO-

12)Propose a synthesis for each of the following compounds starting with benzene.

a. COOH
NO2

COOH

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 Chem. 234 – Chapter 16 Problem Set

b. NH2

Cl

c.

Cl Br

NO2

d. O
NO2

Cl

e. COOH

Cl NO2
Br

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 Chem. 234 – Chapter 16 Problem Set

f.
Cl NO2

g.
Br

O2N

Diazonium Ion Reactions

13)Write out the synthetic sequence to prepare phenol and acetanilide (Ph-NHCOCH3) from
benzene.

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 Chem. 234 – Chapter 16 Problem Set
14)Provide syntheses for each of the following compounds, free of other isomers. Your
starting material should be benzene in each case.

a. Br

OH

b.
I Cl

c. F
Br Br

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 Chem. 234 – Chapter 16 Problem Set

d.

NC

Nucleophilic Aromatic Substitution

15)For each reaction shown below, determine if the reaction is (a) electrophilic aromatic
substitution, (b) Nucleophilic Aromatic Substitution: Addition-Elimination, or (c)
Nucleophilic Aromatic Substitution: Benzyne Mechanism.
Cl
NaOH
a.
350 °C

Cl
NaNH2
b.
NH3

Cl
H 3C NaNH2
c.
NH3

Cl

d. NaOH

NO2

Cl
HNO3
e.
H2SO4

Br
NO2 NaOCH3
f.

NO2

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 Chem. 234 – Chapter 16 Problem Set
16)Show the full electron pushing mechanism for reaction 15c.

17)Show the full electron pushing mechanism for reaction 15d.

18)Explain why the reaction shown below does not occur.

Cl OH
NaOH
Heat
O2N NO 2 O2N NO 2

19)Consider the reaction shown below. Theoretically, there are three possible products. Draw
each of these products. In reality only one of these products is formed. Which one is the
observed product?
Cl
Cl OCH3

NO 2

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 Chem. 234 – Chapter 16 Problem Set
20)Show two methods to synthesize the molecule shown below starting with benzene. One
route should use diazonium ion chemistry while the other route should not.
NO 2

OH

21)Show the reaction of phenol with NaOH.

22)Show the reaction of benzoic acid with NaOH.

23)Is phenol or benzoic acid a stronger acid? Explain.

24)Show the reaction of aniline with HCl.

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 Chem. 234 – Chapter 16 Problem Set
25)Rank the compounds in each set below in order of increasing acidity.

Br O O
NH 2 OH
(a) OH OH

NO 2
OH OH O2N OH
OH
(b)

26)Rank the aniline derivatives below in order of increasing basicity.

NH 2
NH 2 NH 2 NH 2

O2N O
O

Challenge Problems
27)Write a mechanism for the following reaction.
Cl
O

H H
HCl

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 Chem. 234 – Chapter 16 Problem Set
28)Predict the major product for the reaction of pyrrole with Br2, FeBr3. Hint: use resonance
analysis of the intermediate to determine the preferred regioselectivity of the reaction.

H
N Br 2
FeBr 3

29)Show the electron pushing mechanism for the reaction shown below.

OH
NaH NO 2
SO2 O
NO 2
SO2

30)Substituted pyridines are known to undergo nucleophilic aromatic substitution via an

addition elimination mechanism. Predict the product and show the mechanism for the
reaction shown below.
OH

N Br

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