4979-5-22E AID: 1479 | 05/23/2013

RID: 1959 | 12/07/2013

AID: 1112 |4/07/2017

Aromatic halogenation and Friedel-Crafts reactions, are all examples of aromatic

electrophilic substitution reactions.
Acylation of benzene is an example of a Friedel-Crafts reaction. Aluminum trichloride
serves the purpose promoting dissociation of the acyl halide to generate the carbocation
electrophile. The reaction is shown below.
O H
C

CH3COCl

AlCl3

benzene benzaldehyde

(a)

This is an example of a halogenation reaction. The methoxy group -OCH 3 is an ortho-

para directing group. Among the ortho and para products, para product is formed in major
quantity, because para substituted benzaldehyde is more stable due to less repulsions.
Anisole reacts with bromine in the presence of FeBr3 forms a 1-bromo-4-
methoxybenzene.

The reaction is as follows:

CH3 CH3
O O

Br2, FeBr3

Br

Anisole on Friedel-Crafts acylation forms 1-(4-methoxyphenyl)ethanone (a para

derivative).
The reaction is as follows:

CH3 CH3
O O

CH COCl
3
AlCl
3

C
O CH3

anisole 1-(4-methoxyphenyl)ethan-1-one

(b)

The reactant compound is 4-methyl benzaldehyde. The methyl group is an ortho-para

directing group and the aldehyde group is meta directing group.
Here, the two groups methyl and carbonyl direct the incoming electrophile to the same
position. So, a single product is formed on electrophilic substitution.

Therefore, 4-methyl benzaldehyde on halogenation forms 3-bromo-4-

methylbenzaldehyde.
The reaction is as follows:

O H
O H

Br 2
FeBr 3
CH3 directs here CH3 directs here
CHO directs here CHO directs here
Br
CH3
CH3
3-bromo-4-methyl
4-methylbenzaldehyde
benzaldehyde

4-methyl benzaldehyde on Friedel-Crafts acylation forms 3-bromo-4-

methylbenzaldehyde.
The reaction is as follows:
 O H
O H

CH3COCl
AlCl3
CH3 directs here CH3 directs here
CHO directs here CHO directs here COCH3
CH3
CH3
4-methylbenzaldehyde 3-acetyl-4-methylbenzaldehyde