Essential Organic Chemistry (Bruice)

Chapter 7

Essential Organic Chemistry (Bruice)

Chapter 7
Aromaticity: Reactions of Benzene and Substituted Benzenes
1)
The following molecule is not aromatic. Why?

Answer:

It does not have an odd number of pairs of pi electrons (i.e., it does not obey Huckel's rule) and it is not planar.
Section: 7.1

2)
Is the following molecule aromatic? Explain.

Answer:

Yes, it is aromatic since the carbon framework for the system of the molecule is planar, monocyclic with 5 pairs of
electrons.
Section: 7.1

3)
Is the following molecule aromatic? Explain.

Answer:

No, it is not aromatic since the molecule is not a conjugated system.

Section: 7.1

Essential Organic Chemistry (Bruice)

Chapter 7

4)
List the criteria which compounds must meet in order to be considered aromatic.
Answer:

1) The structure must be cyclic.

2) Each atom in the ring must have an unhybridized p orbital.
3) The structure must be planar or nearly planar so that overlap of these p orbitals is effective.
4) The network must contain 4n + 2 electrons (where n is a whole number), so that delocalization of the electrons
results in a lowering of the molecule's electronic energy.
Section: 7.1

5)
Aromatic molecules contain __________ electrons.
A)
no

B)

4n + 2 (with n being an integer)

C)
4n + 2 (with n being 0.5)
D)
4n (with n an integer)
E)
unpaired

Answer:

B
Section: 7.1

6)
Which of the following is an aromatic hydrocarbon?

Essential Organic Chemistry (Bruice)

Chapter 7

A)
I

B)

II

C)

III

D)

IV

E)

Answer:

C
Section: 7.2

7)
Which of the following is aromatic?

A)
I

B)

Essential Organic Chemistry (Bruice)

Chapter 7

II

III

IV

C)

D)

E)

Answer:

C
Section: 7.2

Essential Organic Chemistry (Bruice)

Chapter 7

8)
Which of the following is aromatic?

A)
I

B)

II

C)

III

D)

IV

E)

Answer:

Section: 7.2

9)
Cyclic hydrocarbons which can be represented as structures containing alternating single and double bonds are called
__________.
Answer:

annulenes
Section: 7.2

Essential Organic Chemistry (Bruice)

Chapter 7

10)
Which of the structures below would be aromatic?

A)
I and IV

B)

I, III, and IV
C)
III and IV

II

D)

Answer:

Section: 7.2

11)
Which of the following is aromatic?
A)
cyclopentadienyl cation
B)
1,3-cyclohexadiene
C)
cyclobutenyl anion
D)
1,3,5-hexatriene
E)
cycloheptatrienyl cation
Answer:

Essential Organic Chemistry (Bruice)

Chapter 7

E
Section: 7.2

12)
Which of the following compounds is aromatic?

A)
I

B)

II

C)

III

D)

IV

E)

Answer:

Section: 7.3

13)
Which of the following is aromatic?

Essential Organic Chemistry (Bruice)

Chapter 7

A)
I

II

III

IV

B)

C)

D)

E)

Answer:

A
Section: 7.3

Essential Organic Chemistry (Bruice)

Chapter 7

14)
Provide the structure of the biologically significant heterocycle purine.
Answer:

Section: 7.3

15)
What is the name of the following structure?

Answer:

furan

Section: 7.3

16)
What is the name of the following structure?

Answer:

pyridine
Section: 7.3

17)

Essential Organic Chemistry (Bruice)

Chapter 7

What is the name of the following structure?

Answer:

pyrrole
Section: 7.3

18)
Provide the structure of the biologically significant heterocycle pyrimidine.
Answer:

Section: 7.3

Essential Organic Chemistry (Bruice)

Chapter 7

19)
Provide the structure of indole.
Answer:

Section: 7.3

20)
Provide the structure of anisole.
Answer:

Section: 7.4

21)
Provide the structure of benzenesulfonic acid.
Answer:

Section: 7.4

22)

Essential Organic Chemistry (Bruice)

Chapter 7

Provide the structure of dibenzyl ether.

Answer:

Section: 7.4

Essential Organic Chemistry (Bruice)

Chapter 7

23)
What is the structure of phenol?

A)
I

B)

II

C)

III

D)

IV

E)

Answer:

Section: 7.4

24)
Provide the structure of benzoic acid.
Answer:

Section: 7.4

Essential Organic Chemistry (Bruice)

Chapter 7

25)
Why does benzene undergo electrophilic substitution rather than electrophilic addition?
Answer:

When benzene undergoes electrophilic substitution, the product retains the stability associated with an aromatic system.
This stability is lost in electrophilic addition because the product is not aromatic.
Section: 7.5

26)
Discuss the role of benzene in the first step of an electrophilic aromatic substitution reaction.
Answer:

Benzene is a nucleophile, i.e. the electrons of the benzene ring attack the electrophile and a carbocation results.
Section: 7.5

27)
Describe how the aromatic character of the benzene ring is re-created from the nonaromatic carbocation intermediate
during an electrophilic aromatic substitution reaction.
Answer:

An electron pair donating (Lewis base) species attacks the hydrogen adjacent to the carbocation then the electrons
between this hydrogen and its carbon are donated to the ring to re-create the aromatic benzene ring.
Section: 7.5

Essential Organic Chemistry (Bruice)

Chapter 7

28)
Which of the following is not a correct statement about the electrophilic substitution mechanism of benzene?
A)
Benzene functions as a nucleophile.
B)
Formation of a carbocation intermediate is the rate-determining step.
C)
The carbocation intermediate contains an sp3 hybridized carbon in the ring.
D)
The addition product is a frequently observed minor product.
E)
Aromaticity is regained by loss of H+.
Answer:

Section: 7.5

29)
Which of the following is most likely to be the first step in the general mechanism for electrophilic substitution reactions?

A)
I

II

III

B)

C)

D)

Essential Organic Chemistry (Bruice)

Chapter 7

IV

E)

Answer:

B
Section: 7.6

30)
Provide the major resonance structures of the intermediate sigma complex in the reaction of benzene with the generic
electrophile E+.
Answer:

Section: 7.6

31)
Which step in the general mechanism for electrophilic aromatic substitution is rate-determining? Explain.
Answer:

The first step involves addition of the electrophile to benzene to yield a nonaromatic cationic intermediate. The second
step involves the loss of H+ from this cationic intermediate to yield an aromatic product. The rate-determining or slow
step is the one in which the aromatic reagent is converted into a much less stable nonaromatic cation.
Section: 7.6

32)
In the bromination of benzene using Br2 and FeBr3, is the intermediate carbocation aromatic? Explain.
Answer:

No, the carbocation is not aromatic since the ring contains an sp3 center.
Section: 7.6 and 7.7

Essential Organic Chemistry (Bruice)

Chapter 7

33)
Which of the following is one of the resonance contributors of the intermediate produced in a Friedel-Crafts alkylation of
benzene?

A)
I

B)

II

C)

III

D)

IV

E)

Answer:

A
Section: 7.6 and 7.11

34)
Which of the following is the first step in the mechanism of bromination?

A)

Essential Organic Chemistry (Bruice)

Chapter 7

II

III

IV

B)

C)

D)

E)

Answer:

C
Section: 7.7

Essential Organic Chemistry (Bruice)

Chapter 7

35)
Provide a detailed, stepwise mechanism for the reaction of benzene with Br2 and FeBr3. Make sure to include the
activating reaction between Br2 and FeBr3 in your mechanism.
Answer:

Section: 7.7

36)
Bromination of benzene requires a Lewis acid catalyst while bromination of cyclohexene does not. Explain this difference
in reactivity.
Answer:

An alkene is a better nucleophile than benzene, and thus the Br-Br bond does not have to be weakened to form a better
electrophile before reaction.
Section: 7.7

37)
What purpose does FeCl3 serve in the electrophilic aromatic substitution reaction between chlorine and benzene?
A)

It serves as a radical initiator to produce the chlorine radical needed to propagate the chain reaction.
B)
It functions by destabilizing the carbocationic intermediate and thereby increases the rate of H + loss.
C)

Essential Organic Chemistry (Bruice)

Chapter 7

It serves as a Lewis base catalyst by reacting with Cl2 to generate chloride ions.
D)

It functions by destabilizing the benzene through formation of a -complex.

E)
It serves as a Lewis acid catalyst by reacting with the Cl2 and thereby activates it toward attack by benzene's electrons.
Answer:

E
Section: 7.7

38)
Explain the role of nitric acid and sulfuric acid in the first step in the nitration of benzene.
Answer:

A hydrogen from sulfuric acid protonates the hydroxy group of the nitric acid forming a molecule of water which is then
a good leaving group, thereby forming the nitronium ion (NO2+)(the electrophile).

Section: 7.8

39)
Which of the following is the electrophile that attacks the aromatic ring during nitration?
A)
NO2

HNO3

B)

C)

D)

Essential Organic Chemistry (Bruice)

Chapter 7

E)

Answer:

Section: 7.8

40)
Which of the following is the electrophile that attacks the aromatic ring during sulfonation?
A)

B)

C)

D)
H2SO4

E)

Answer:

A
Section: 7.9

41)

Essential Organic Chemistry (Bruice)

Chapter 7

Which of the following is the electrophile that attacks the aromatic ring during Friedel-Crafts acylation?
A)

B)

C)

D)

E)
AlCl3

Answer:

Section: 7.10

42)
What is the role of AlCl3 in Friedel-Crafts acylation of benzene and Friedel-Crafts akylation of benzene?
Answer:

AlCl3 reacts with the acyl chloride in the acylation to give an acylium ion and -AlCl4. AlCl3 reacts with the alkyl halide
to give a carbocation and -AlCl4.
Section: 7.10 and 7.11

43)
Which of the following is not a correct statement concerning the Friedel-Crafts acylation of benzene?
A)

Essential Organic Chemistry (Bruice)

Chapter 7

An alkyl group substitutes for a hydrogen.

B)
The benzene ring attacks an acylium ion.
C)
The acylium ion is resonance stabilized.
D)
The acylium ion is often produced from an acyl chloride.
E)
More than one equivalent of Lewis acid must be used.
Answer:

A
Section: 7.10

44)
What is the major product of the following Friedel-Crafts alkylation?

A)
I

II

B)

C)

Essential Organic Chemistry (Bruice)

Chapter 7

III

IV

D)

E)

Answer:

C
Section: 7.11

Essential Organic Chemistry (Bruice)

Chapter 7

45)
What is the major organic product of the reaction between benzene and isobutyl chloride in the presence of AlCl 3?
A)

tert-butylbenzene
B)
isobutylbenzene
C)
n-butylbenzene
D)
chlorobenzene
E)
sec-butylbenzene
Answer:

Section: 7.11

46)
What is the name of the following compound?

A)
m-Bromomethylbenzene
B)
m-Bromotoluene
C)
3-Bromotoluene
D)
A and B

E)

Essential Organic Chemistry (Bruice)

Chapter 7

B and C

Answer:

E
Section: 7.12

47)
What is the structure of 3-phenylpentane?

A)
I

B)

II

C)

III

D)

IV

E)

Answer:

Section: 7.12

48)

Essential Organic Chemistry (Bruice)

Chapter 7

What is the name of the following compound?

A)
p-Dichlorobenzene
B)
1,4-Dichlorobenzene
C)
Phenyldichloride
D)
A and B

B and C

E)

Answer:

Section: 7.12

49)
What is the structure of p-toluidine?

A)
I

B)

Essential Organic Chemistry (Bruice)

Chapter 7

II

III

IV

C)

D)

E)

Answer:

C
Section: 7.12

Essential Organic Chemistry (Bruice)

Chapter 7

50)
What is the name of the following compound?

A)
o-nitro-m-bromotoluene
B)
3-bromo-6-nitrotoluene
C)
m-bromo-o-nitrotoluene
D)
5-bromo-2-nitrotoluene
E)
2-nitro-5-bromotoluene
Answer:

Section: 7.12

51)
The name 2,4,6-tribromobenzene is incorrect. Which of the following is the correct name?
A)
tribromobenzene
B)
m,m-dibromobromobenzene
C)
3,5-dibromobromobenzene
D)
1,3,5-tribromobenzene
E)
m,m,m-tribromobenzene

Essential Organic Chemistry (Bruice)

Chapter 7

Answer:

D
Section: 7.12

52)
What is the proper name of the compound below?

A)
1-phenoxyethane
B)
ethyl phenyl ether
C)
m-sec-butylhydroxybenzene
D)
o-butylhydroxybenzene
E)
m-butylphenol
Answer:

Section: 7.12

53)
Provide the best name for the organic compound below.

Answer:

Essential Organic Chemistry (Bruice)

Chapter 7

o-propylphenol or 2-propylphenol
Section: 7.12

54)
Provide the best name for the organic compound below.

Answer:

m-toluidine

Section: 7.12

55)
Which of the following compounds reacts most slowly during nitration?

A)
I

II

III

IV

B)

C)

D)

E)

Essential Organic Chemistry (Bruice)

Chapter 7

Answer:

C
Section: 7.13

56)
Which of the following compounds reacts most rapidly during nitration?

A)
I

B)

II

C)

III

D)

IV

E)

Answer:

Section: 7.13

57)
Which of the following substrates is an electron donating group overall?
A)
Br

Essential Organic Chemistry (Bruice)

Chapter 7

B)

C)
OCH3

D)

E)
CCl3

Answer:

Section: 7.13

58)
Which of the following substrates is an electron withdrawing group overall?

A)
I

II

III

IV

B)

C)

D)

E)

Essential Organic Chemistry (Bruice)

Chapter 7

Answer:

E
Section: 7.13

59)
Rank the following groups in order of increasing activating power in electrophilic aromatic substitution reactions:
-OCH3, -OCOCH2CH3, -CH2CH3, -Br.
Answer:

-Br < -CH2CH3 < -OCOCH2CH3 < -OCH3

Section: 7.13

60)
Which of the following compounds reacts most rapidly with HNO3/H2SO4?
A)

toluene

anisole

B)

C)

nitrobenzene
D)
benzonitrile

E)

fluorobenzene
Answer:

Section: 7.13

61)
List the following compounds in order of decreasing reactivity toward electrophilic aromatic substitution: toluene,
benzene, fluorobenzene, nitrobenzene, phenol.
Answer:

Essential Organic Chemistry (Bruice)

Chapter 7

phenol > toluene > benzene > fluorobenzene > nitrobenzene

Section: 7.13

62)
Which of the following substituents acts as a moderate activator and o/p director in electrophilic aromatic substitution
reactions?
A)
-Br
B)
-SO3H

-CO2H

C)

D)

-NHC(=O)R
E)
-CHO
Answer:

Section: 7.13

63)
Which of the following structures is the most important contributor to the resonance hybrid formed when toluene
undergoes para nitration?

Essential Organic Chemistry (Bruice)

Chapter 7

A)
I

II

III

IV

B)

C)

D)

E)

Answer:

Section: 7.14

Essential Organic Chemistry (Bruice)

Chapter 7

64)
Which of the following structures is the most important contributor to the resonance hybrid formed when anisole
undergoes o-bromination?

A)
I

B)

II

C)

III

D)

IV

E)

Answer:

Section: 7.14

65)
What is the major product of the following reaction?

Essential Organic Chemistry (Bruice)

Chapter 7

A)
I

B)

II

C)

III

D)

IV

E)

Answer:

C
Section: 7.14

66)
In electrophilic aromatic substitution reactions a chlorine substituent:
A)
is a deactivator and a m-director.
B)
is a deactivator and an o,p-director.
C)
is an activator and a m-director.
D)

Essential Organic Chemistry (Bruice)

Chapter 7

is an activator and an o,p-director.

E)
none of the above
Answer:

B
Section: 7.14

67)
Draw the four major resonance structures of the carbocation intermediate in the reaction of anisole with HNO 3/H2SO4 to
yield p-nitroanisole.
Answer:

Section: 7.14

68)
Draw the three major resonance structures of the carbocation intermediate in the reaction of acetophenone with
HNO3/H2SO4 to yield o-nitroacetophenone. Circle the resonance form which is less stable than the other two.
Answer:

Section: 7.14

69)
Compare the effect of electron withdrawing group on an alcohol relative to that of an electron donating group on an

Essential Organic Chemistry (Bruice)

Chapter 7

alcohol.

Answer:

An electron withdrawing group stabilizes a base and increases the strength of its conjugate acid while an electron
donating group destabilizes a base and decreases the strength of its conjugate acid. Thus electron withdrawing groups on
an alcohol will increase the acidity of the alcohol.
Section: 7.15

Essential Organic Chemistry (Bruice)

Chapter 7

70)
List the following compounds in order of decreasing basicity.

Answer:

Section: 7.15

71)
List the following compounds in order of decreasing acidity.

Answer:

Section: 7.15