Reactions of

Aromatic Compounds
TEMA 6
Qumica Orgnica 2014

Electrophilic
Aromatic Substitution
Electrophile substitutes for a hydrogen
on the benzene ring.

=>
Chapter 17

Unusual Stability
Hydrogenation of just one double
bond in benzene is endothermic!

=>
Chapter 17

Mechanism

=>
4

Bromination of Benzene
Requires a stronger electrophile than Br2.
Use a strong Lewis acid catalyst, FeBr3.
Br Br

FeBr3

H
H

Br
H

Br

FeBr3

+
H

Br

FeBr3

Br
Br

_
+ FeBr4

H
H

Br
+

HBr

=>
5

Energy Diagram for

Bromination

Chapter 17

=>
6

Chlorination
and Iodination
Chlorination is similar to bromination.
Use AlCl3 as the Lewis acid catalyst.
Iodination requires an acidic oxidizing
agent, like nitric acid, which oxidizes the
iodine to an iodonium ion.
+

+ HNO 3 + 1/2 I2

NO2 + H2O
=>
7

Nitration of Benzene
Use sulfuric acid with nitric acid to form
the nitronium ion electrophile.
O
H O

O H

H O

H O N

H O N
+
O

H O
H O N
+
O

O
H2O +

N+
O

_
+ HSO4

NO2+ then forms a

sigma complex with
benzene, loses H+ to
form nitrobenzene. =>
8

Sulfonation
Sulfur trioxide, SO3, in fuming sulfuric acid
is the electrophile.
O

S+
O
O

S+
_
O
O
_

O
S
O

H O
S O
+
O
H

S +
O
O
HO

S
O

benzenesulfonic acid

=>
9

Desulfonation
All steps are reversible, so sulfonic acid
group can be removed by heating in
dilute sulfuric acid.
This process is used to place deuterium
in place of hydrogen on benzene ring.
D

H
H

H
H

large excess
D2SO4/D2O

=>

Benzene-d6

10

Nitration of Toluene
Toluene reacts 25 times faster than benzene.
The methyl group is an activator.
The product mix contains mostly ortho and
para substituted molecules.

=>
11

Sigma Complex
Intermediate
is more
stable if
nitration
occurs at
the ortho
or para
position.

=>

12

Energy Diagram

=>
13

Activating, O-, PDirecting Substituents

Alkyl groups stabilize the sigma complex by
induction, donating electron density through
the sigma bond.
Substituents with a lone pair of electrons
stabilize the sigma complex by resonance.
+

OCH3

+
OCH3

NO 2

NO 2

=>
14

The Amino Group

Aniline reacts with bromine water (without a
catalyst) to yield the tribromide. Sodium
bicarbonate is added to neutralize the
HBr thats also formed.
NH2

NH2

Br

Br

3 Br2
H2O, NaHCO3
Br

=>
15

Summary of
Activators

16

=>

Deactivating MetaDirecting Substituents

Electrophilic substitution reactions for
nitrobenzene are 100,000 times slower
than for benzene.
The product mix contains mostly the
meta isomer, only small amounts of the
ortho and para isomers.
Meta-directors deactivate all positions
on the ring, but the meta position is less
deactivated.
=>17

Ortho Substitution
on Nitrobenzene

=>
18

Para Substitution
on Nitrobenzene

=>
19

Meta Substitution
on Nitrobenzene

=>
20

Energy Diagram

=>
Chapter 17

21

Structure of MetaDirecting Deactivators

The atom attached to the aromatic ring
will have a partial positive charge.
Electron density is withdrawn inductively
along the sigma bond, so the ring is less
electron-rich than benzene.
=>
22

Summary of Deactivators

=>
23

More Deactivators

=>
24

Halobenzenes
Halogens are deactivating toward
electrophilic substitution, but are ortho,
para-directing!
Since halogens are very electronegative,
they withdraw electron density from the
ring inductively along the sigma bond.
But halogens have lone pairs of electrons
that can stabilize the sigma complex by
resonance.
=>
25

Sigma Complex
for Bromobenzene
Para attack

Ortho attack
Br

Br

(+)

Br

Br

(+)

H
E

(+)

(+)

(+)

E+

(+)

H E

Ortho and para attacks produce a bromonium ion

and other resonance structures.
Meta attack

Br

Br

(+)

(+)

No bromonium ion
possible with meta attack.

=>
26

Energy Diagram

=>
27

Summary of
Directing Effects

28

=>

Multiple Substituents
The most strongly activating substituent
will determine the position of the next
substitution.
substitution May have mixtures.
OCH3

OCH3

SO3H

SO3
O2N

H2SO4

OCH3
+

O2N

O2N
SO3H

P-isomer ?

=>
29

Friedel-Crafts Alkylation
Synthesis of alkyl benzenes from alkyl
halides and a Lewis acid, usually AlCl3.
Reactions of alkyl halide with Lewis acid
produces a carbocation which is the
electrophile.
Other sources of carbocations:
alkenes + HF or alcohols + BF3.
=>
30

Examples of
Carbocation Formation
Cl
CH3

CH CH3

+ AlCl3

_
CH3 +
C Cl AlCl3
H3C H

H2C

OH
H3C

CH CH3

CH CH3

BF3

HF

+ BF3
H O
H3C

CH CH3

F
+
H3C CH CH3

_
+
H3C CH CH3 + HOBF3

=>
31

Formation of
Alkyl Benzene
CH3
+C

CH3

F
H
+

CH(CH3)2
H

CH(CH3)2

B OH

CH3

CH
+
CH3

HF
F
F

B OH

=>
32

Limitations of
Friedel-Crafts
Reaction fails if benzene has a substituent
that is more deactivating than halogen.
halogen
Carbocations rearrange. Reaction of
benzene with n-propyl chloride and AlCl3
produces isopropylbenzene.
The alkylbenzene product is more reactive
than benzene, so polyalkylation occurs.
=>
33

Friedel-Crafts
Acylation
Acyl chloride is used in place of alkyl
chloride.
The acylium ion intermediate is
resonance stabilized and does not
rearrange like a carbocation.
The product is a phenyl ketone that is
less reactive than benzene.
=>
34

Mechanism of Acylation
O
R C Cl

+ _
R C Cl AlCl3

AlCl3

+ _
R C Cl AlCl3

_
AlCl4
O

C+
R

+
R C O

Cl

_
AlCl3

+
R C O
O
C

HCl
R +

AlCl3

=>
35

Clemmensen Reduction
Acylbenzenes can be converted to
alkylbenzenes by treatment with
aqueous HCl and amalgamated zinc.
O
O
+ CH3CH2C

Cl

1) AlCl3
2) H2O

C CH2CH3

Zn(Hg)

CH2CH2CH3

aq. HCl

=>
36

Arenes
Alkylbenzenes
Alkenylbenzenes
Alkynylbenzenes

37

Side-Chain Oxidation
Alkylbenzenes are oxidized to benzoic
acid by hot KMnO4 or Na2Cr2O7/H2SO4.
CH(CH3)2

KMnO4, OH

CH CH2

Not t-butylbenzene

H2O, heat

_
COO
_
COO

=>
38

Side-Chain Halogenation
Benzylic position is the most reactive.
Chlorination is not as selective as
bromination, results in mixtures.
Br2 reacts only at the benzylic position.
Br
CH2CH2CH3
Br2, h

CHCH2CH3

=>
39

Benzyl Radical

40