Chapter 16Chemistry of Benzene: Electrophilic Aromatic Substitution

SHORT ANSWER

Exhibit 16-1
MATCH a structure or term from the following list with each description below. Place the letter of
the structure or term in the blank to the left of the description.
+
a. benzyne e. NO
+
b. NO2 f. Meisenheimer complex
c. R3C+ g.
d. electron-donating h. electron-withdrawing
i. F-TEDA-BF4

1. ______ The reactive electrophile in Friedel-Crafts acylation reactions.

ANS:
g

2. ______ The electrophile in aromatic nitration.

ANS:
b

3. ______ Groups which activate aromatic rings towards electrophilic substitution.

ANS:
d

4. ______ Groups which activate aromatic rings towards nucleophilic substitution.

ANS:
h

5. ______ Intermediate in the elimination-addition mechanism of nucleophilic aromatic

substitution.

ANS:
a

6. __________Source of F+ in fluorination reactions.

ANS:
i

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Chemistry of Benzene: Electrophilic Aromatic Substitution

Exhibit 16-2
Consider the Friedel-Crafts alkylation reaction below to answer the following question(s):

7. Refer to Exhibit 16-2. Draw the structure of the electrophilic intermediate in this reaction.

ANS:

8. Refer to Exhibit 16-2. What is the role of the AlCl3 in the reaction?

ANS:
The AlCl3 is a Lewis acid catalyst that assists in the ionization of the alkyl halide to give the
carbocation electrophile.

9. Refer to Exhibit 16-2. Write the complete stepwise mechanism for this reaction. Show all
electron flow with arrows and include all intermediate structures.

ANS:

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 Chapter 16

10. Aniline reacts with nitrous acid, HNO2, to yield a stable diazonium salt. This diazonium salt
undergoes electrophilic aromatic substitution on activated aromatic rings to yield brightly
colored azo compounds that are widely used as dyes. The intermediate structures for the
mechanism of this reaction are given below. Show all electron flow with arrows for this
mechanism on the structures provided.

ANS:

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Chemistry of Benzene: Electrophilic Aromatic Substitution

Exhibit 16-3
Consider the data below to answer the following question(s).

The NH2 group is listed in our textbook as the strongest o,p-directing activator in electrophilic
aromatic substitution reactions. However, when aniline is subjected to standard nitration
conditions poor yields of m-nitroaniline result.

11. Refer to Exhibit 16-3. Draw all the resonance forms of aniline showing the electron-
donating effect of the NH2 substituent.

ANS:

12. Refer to Exhibit 16-3. Clearly, the reaction conditions are influencing the directing effect of
the NH2 group. Explain why this occurs, using both words and structures.

ANS:

When aniline is placed in strong acid the nitrogen atom is protonated. Electrophilic aromatic
substitution on the anilinium ionwhose aromatic ring is now deactivated by a positively charged
substituentoccurs primarily at the meta position since this keeps the positive charge of the
intermediate carbocation away from the positively charged nitrogen. The intermediates shown
above for ortho and para substitution are destabilized more than the intermediate for meta
substitution, so m-nitroaniline is the major product.

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 Chapter 16

Exhibit 16-4
Consider the reaction below to answer the following question(s).

13. Refer to Exhibit 16-4. Write the complete stepwise mechanism for the formation of the
ortho product. Show all intermediate structures and show all electron flow with arrows.

ANS:

14. Refer to Exhibit 16-4. Draw resonance structures for the intermediate carbocation that
explain the directing effect of the Br.

ANS:

Exhibit 16-5
Rank the compounds in each group below according to their reactivity toward electrophilic
aromatic substitution (most reactive = 1; least reactive = 3). Place the number corresponding to the
compounds' relative reactivity in the blank below the compound.

15.

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Chemistry of Benzene: Electrophilic Aromatic Substitution

ANS:

16.

ANS:

17. At what position, and on what ring, is bromination of phenyl benzoate expected to occur?
Explain your answer.

ANS:

Attack occurs in the activated ring and yields ortho and para bromination.

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 Chapter 16

Exhibit 16-6
To answer the following question(s), refer to the data below:

Isobutylbenzene is the starting material for the industrial synthesis of the NSAID, ibuprofen.

18. Refer to Exhibit 16-6. Attempts to prepare isobutylbenzene by direct Friedel-Crafts

alkylation of benzene result in tert-butylbenzene as the major product. Write the complete
stepwise mechanism for this reaction, showing all electron flow with arrows and showing all
intermediate structures.

ANS:

19. Refer to Exhibit 16-6. Propose a synthesis for isobutylbenzene which avoids the problems of
direct Friedel-Crafts alkylation.

ANS:

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Chemistry of Benzene: Electrophilic Aromatic Substitution

20. Would you expect (nitromethyl)benzene to be more reactive or less reactive than toluene
toward electrophilic substitution? Explain.

ANS:
(Nitromethyl)benzene should be less reactive than toluene owing to the strong inductive electron
withdrawing effect of the nitro group.

Exhibit 16-7
Consider the reaction below to answer the following question(s).

21. Refer to Exhibit 16-7. The nucleophile in the reaction is:

ANS:
A

22. Refer to Exhibit 16-7. The Lewis acid catalyst in the reaction is:

ANS:
C

23. Refer to Exhibit 16-7. This reaction proceeds _____ (faster or slower) than benzene.

ANS:
slower

24. Refer to Exhibit 16-7. Draw the structure of product D.

ANS:

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 Chapter 16

25. The following reaction proceeds by an intramolecular nucleophilic aromatic substitution

mechanism. Write the complete stepwise mechanism, showing all intermediate structures
and all electron flow with arrows.

ANS:

26. Tetracyclone is often used to trap benzynes as Diels-Alder adducts. What is the structure of
the Diels-Alder adduct that results when benzyne is trapped by tetracyclone?

ANS:

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Chemistry of Benzene: Electrophilic Aromatic Substitution

27. On the structural intermediates below, show all electron flow with arrows for the
nucleophilic aromatic substitution reaction of p-nitrochlorobenzene with KOH.

ANS:

Exhibit 16-8
Give the major organic product(s) of each of the following reactions. If none is predicted, write
"N.R."

28.

ANS:

29.

ANS:
N.R. Nucleophilic Aromatic Substitution requires an electron-withdrawing group in the ortho or
para position. A methyl group is electron donating, and substitution will not occur.

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 Chapter 16

30.

ANS:

31.

ANS:

32.

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Chemistry of Benzene: Electrophilic Aromatic Substitution

ANS:

33.

ANS:

34.

ANS:

35.

ANS:

12
 Chapter 16

36.

ANS:

37.

ANS:

38.

ANS:

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Chemistry of Benzene: Electrophilic Aromatic Substitution

39.

ANS:

40.

ANS:

(Friedel-Crafts reactions do not proceed in the presence of a deactivating group)

41.

ANS:

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 Chapter 16

42.

ANS:

43.

ANS:

44.

ANS:

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Chemistry of Benzene: Electrophilic Aromatic Substitution

Exhibit 16-9
Choose the best reagent(s) from the list provided below for carrying out the following conversions.
Place the letter of the reagent in the box beside the reaction number over the arrow. There is only
one answer for each reaction.

a. KMnO4, H3O+ f. ClCO(CH2)2CH3, AlCl3

b. Br2, FeBr3 g. CH3CH2CH2CH2Cl, AlCl3
c. Cl2, FeCl3 h. H2/Pd
d. CH3Cl, AlCl3 i. NBS, peroxides
e. HNO3, H2SO4 j. (CH3)3CCH2Cl
k. F-TEDA-BF4

45.

ANS:

46.

ANS:

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 Chapter 16

47.

ANS:

48.

ANS:

49.

ANS:

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Chemistry of Benzene: Electrophilic Aromatic Substitution

Exhibit 16-10
Propose syntheses to carry out each of the following conversions. Assume ortho and para isomers
can be separated.

50.

ANS:

51.

ANS:

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 Chapter 16

52.

ANS:

53.

ANS:

54.

ANS:

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Chemistry of Benzene: Electrophilic Aromatic Substitution

55.

ANS:

Exhibit 16-11
Propose syntheses of the following compounds starting with benzene or toluene. Assume ortho
and para isomers can be separated.

56.

ANS:

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 Chapter 16

57.

ANS:

58. It is possible to synthesize 1-bromo-4-nitrobenzene by reacting bromobenzene with a

mixture of nitric and sulfuric acids. However, 1-bromo-4-nitrobenzene is not obtained if
nitrobenzene is reacted with Br2/FeBr3. Explain the difference.

ANS:
Bromine is an ortho-para director. The para isomer preferentially forms on nitration due to the
steric hindrance of the bulky Br group. The result is a good yield of 1-bromo-4-nitrobenzene.
NO2 is a meta director and preferentially forms the meta isomer on bromination. The resulting
product is the meta isomer or 1-bromo-3-nitrobenzene.

MULTIPLE CHOICE

1. Which of the following could successfully undergo a Friedel-Crafts alkylation? Assume an

appropriate catalyst.
a. chlorobenzene reacting with benzene
b. 2-chloroethene reacting with benzene
c. 2-chloropropane reacting with benzaldehyde
d. 2-chlorobutane reacting with benzene
ANS: D

2. Which of the following is an ortho- and para- director?

a. NO2 c. CN
b. NH2 d. CO2CH3
ANS: B

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Chemistry of Benzene: Electrophilic Aromatic Substitution

3. Which of the following is a meta- director?

a. OH c. CH2CH2CH3
b. Br d. COCH3
ANS: D

4. Which of the following is a deactivating group?

a. CO2H c. OH
b. I d. CH3
ANS: A

5. Which of the following is an ortho- and para- director and a deactivator?

a. NO2
b. F
c. CN
d. CH2CH3
e. none of these
ANS: B

6. What is(are) the product(s) when the following substance reacts with Br2 in the presence of
FeBr3?

a. o-bromotoluene
b. m-bromotoluene
c. p-bromotoluene
d. an equimolar mixture of o-bromotoluene and p-bromotoluene
e. a mixture of o-bromotoluene (minor) and p-bromotoluene (major)
f. a mixture of o-bromotoluene (major) and p-bromotoluene (minor)
ANS: E

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 Chapter 16

7. Arrange the following compounds in order of increasing reactivity to electrophilic aromatic

substitution.

bromobenzene nitrobenzene benzene phenol

a. phenol < benzene < bromobenzene < c. nitrobenzene < bromobenene < benzene <
nitrobenzene phenol
b. bromobenzene < nitrobenzene < benzene d. nitrobenzene < benzene < bromobenzene
< phenol < phenol
ANS: C

8. When the following compound is treated with a mixture of nitric and sulfuric acids, which of
the following will be produced?

a. 5-chloro-2-nitrotoluene
b. 3-chloro-4-nitrotoluene
c. 3-chloro-2-nitrotoluene
d. 5-chloro-3-nitrotoluene
e. a mixture of 3-chloro-4-nitrotoluene (major) and 5-chloro-2-nitrotoluene (minor)
f. an equimolar mixture of 3-chloro-2-nitrotoluene, 5-chloro-2-nitrotoluene, and 3-chloro-4-
nitrotoluene
g. a mixture a, b, c, and d
ANS: E

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