CHAPTER 4

AROMATIC
COMPOUNDS
1
 4.1
Introduction to
Aromatic
Compounds

2
 Aromatic Compounds

• In chemistry, the word aromatic is related to the unusual

stability of benzene or its derivatives.
• Aromatic compound is a cyclic compound (molecule or
ion) with conjugated double bonds, having unusually
large resonance energy and is stabilized by the 
electron delocalisation.
• Aromatic hydrocarbons that contain a benzene ring as a
structural unit (derivatives of benzene) are called
arenes.

3
• It is characterized by substitution reactions.
• Some examples of aromatic compound are :

Benzene : Toluene : CH3

Naphthalene :

• Benzene, C6H6 is the simplest aromatic hydrocarbon.

4
 Criteria for aromaticity
• Aromatic compound must obey following criteria:

Cyclic • All p orbitals overlap each other

Planar •  electrons can be delocalized

Completely conjugated
double bonds • Every atom has unhybridized p orbital

HÜckel’s Rule • Obeys HÜckel’s Rule

5
 Hückel’s Rule
• Hückel’s Rule state that the system is aromatic if the
number of pi () electrons is 4n+2 where n = 0, 1, 2, 3…
• Example:

n Number of  electrons (4n+2)

0 2
1 6
2 10
3 14
4 18
6
Example 1:
Identify which of the following are aromatic compound :
●● ―

Answer :

Both structures are aromatic compound because:

▪ They are cyclic, planar and have conjugated double bonds
in the ring
▪ They obey HÜckels Rule (has 6π electrons )

7
Example 2:
Identify the aromaticity of the compounds below:

a. b. c.

_
d. e. f.

8
 4.2
Nomenclature of
benzene and its
derivatives

9
• Many organic molecules contain a benzene
ring with one or more substituents.
• Example :

F NO2
NO2

monosubstituent disubstituent

10
 Mono-substituted benzene

• Benzene is the parent name and the substituent is

indicated by a prefix.
• Example:
F NO 2

Cl Br

fluorobenzene nitrobenzene

chlorobenzene bromobenzene
11
• IUPAC rules allow some common names to be retained as
follows :
CH3 OH NH2 SO 3H

toluene phenol aniline benzenesulfonic acid

O
COOH CHO
C CH3

benzoic acid acetophenone benzaldehyde 12

 Di-substituted benzene

i. Two same substituents

• Relative position of subsituents are indicated

by prefixes ortho, meta, and para
(abbreviated by o–, m–, and p–) or by the
use of number.

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 • Example :
Br Br
1
1 Br 2
2
3
Br
Br
1,2–dibromobenzene 1 1,3–dibromobenzene
or 2 or
o–dibromobenzene m–dibromobenzene
3
4
Br

1,4–dibromobenzene
or
p–dibromobenzene
14
• Example :
NO2
NO2 1
1 2
2 NO2
3
4
NO2
1,2–dinitrobenzene
or 1,4–dinitrobenzene
o–dinitrobenzene NO2 or
1 p–dinitrobenzene
2

3
NO2
1,3–dinitrobenzene
or
m–dinitrobenzene 15
ii. Two different substituents

• When two different substituents are present,

choose one of the substituent that give
new parent name (common name) and
numbered as C1.

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COOH 2–nitrobenzoic acid
1 NO2 or
2 o–nitrobenzoic acid

COOH
1 3–nitrobenzoic acid
2 or
3 m–nitrobenzoic acid
NO2

COOH
1
2 4–nitrobenzoic acid
or
3 p–nitrobenzoic acid
4
NO2 17
• if no common name is applicable, give the lowest
possible number to the substituents and list them in
alphabetical order.
• Example:

CH2CH3
4
3 1-chloro-4-ethylbenzene
or
2
p-chloroethylbenzene
1
Cl

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NO 2
4
3 1-chloro-4-nitrobenzene
or
2
1
p-chloronitrobenzene
Cl

Br
1 1-bromo-3-chlorobenzene
2 or
m-bromochlorobenzene
3 Cl

19
 Benzene ring as substituent

• Example of benzene substituents:

CH2—

phenyl group benzyl group

CH2Br CH2OH

benzyl bromide benzyl alcohol 20

• Benzene ring is a substituent , called phenyl when:
a) it is attached to a carbon chain containing
functional group.

1 2 3 4
CH2–C C–CH3 CH2–CH2–OH

1–phenyl–2–butene 2–phenylethanol

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b) attached to a chain containing six or more
carbon atoms

• the compound is named as phenyl-

substituted alkane.

1 CH2

CH–CH2–CH2–CH2–CH2–CH3
2 3 4 5 6 7

2–phenylheptane

• phenyl can be written as C6H5– or Ph

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 4.3
Chemical properties
of benzene and its
derivatives

23
• Reaction of benzene occur at the benzene ring as
the reaction site while its derivatives have the
side-chain reactions.
• It’s closed shell of six  electrons gives a special
stability thus benzene does not undergo addition
reactions as alkene.
• In fact it undergoes substitution reaction.

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• Example :

Br
FeBr3
+ Br2
benzene bromobenzene

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4 aromatic substitutions reaction are :
NO2
HNO3 conc.
+ H2 O
H2SO4 conc. nitration
50-55oC

X
X2, FeX3
+ HX halogenation
(X = Cl or Br)

R
RCl , AlCl3 Friedel-Crafts
(R can rearrange) + HCl Alkylation

O
O C–R Friedel-Crafts
RCCl , AlCl3 Acylation
+ HCl
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 (i) Halogenation
• Benzene reacts with bromine or chlorine in the presence
of a Lewis acid.
• The Lewis acids commonly used are FeCl3, AlCl3 for
chlorination and FeBr3 for bromination.

X
+ X2 Fe or FeX3 + HX

• Example:
FeBr3 Br
+ Br2 + HBr
bromobenzene 27
• Function of Lewis acid:
i. Increase the polarity of halogen molecules.
ii. Produce positive halogen ions (Br+ or Cl+).

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 (ii) Nitration of benzene

• It involves the substitution of nitro group to H atom of

benzene.
• Benzene reacts rapidly with a mixture of concentrated
nitric acid and concentrated sulphuric acid to give
nitrobenzene.

NO2
conc. HNO3 , conc. H2SO4
50-55oC
+ H+ + HSO4–

nitrobenzene

29
 (iii) Friedel – Crafts alkylation

• Alkylation is the substitution of an alkyl group to H atom

of benzene.
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• Benzene reacts with haloalkane, R–X in the presence of
Lewis acid such as AlCl3 or FeCl3 as a catalyst to form
an alkylbenzene.

R
AlCl3
+ R–X + HCl
alkylbenzene

• The haloalkane molecule is polarised by catalyst which

dissociates to give a carbocation. The carbocation
formed acts as an electrophile.

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• Example:

Cl CH(CH3)2
AlCl3
+ CH3CHCH3 + HCl
2–chloropropane
isopropylbenzene

AlCl3
C(CH3)3
+ (CH3)3C–Cl + HCl
2–chloro–2–methylpropane
tert–butylbenzene

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Exercise:
1. Draw the structure of the product formed when benzene is
treated with each organic halide below in the presence of
AlCl3. O

Cl C
a. (CH 3)2CHCl b. c. H3C CH2 Cl

33
34
 (iii) Friedel – Crafts acylation
O

• The R C group is called an acyl group.

• The reaction whereby the acyl group is introduced into
a compound is called an acylation reaction.
• The examples of acyl groups are:

O O

CH3C C

acetyl group
(ethanoyl group) benzoyl group

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• Benzene reacts with acyl chloride in the presence of Lewis
acid catalyst such as AlCl3 produces acylbenzene.
O
O C
AlCl3 R
+ R C Cl
+ HCl

• Example:
O
O
AlCl3 CCH3
+ CH3C—Cl + HCl
acetyl chloride
acetophenone

Acylation = substitute an acyl group to H atom of benzene

36
 Exercise:
1. Draw the structure of acyl chloride used to prepare each
of the following ketones from benzene through Friedel-
Crafts acylation.
a. O b. O c. O
C CH2 CH2 CH CH3 C C
CH3

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