Aromatic Hydrocarbon

Kekule structure
Kekule suggested that the carbon atoms of
benzene ring are in the ring, bonded to each
other by alternating single and double bonds.

H
H H Kekule
OR Structure
H H
H

However, Kekule structure can’t explain why benzene

molecules are not undergoes addition reaction.
Resonance Structure
In 1930s , Linus Pauling introduced the concept
of hybrid orbital and resonance.
The real structure of benzene is the resonance
hybrid from two Kekulé structure as shown below:

Hybrid resonance
structure
 NOMENCLATURE
1. naming monosubstituted benzene

F Cl NO2

florobenzene chlorobenzene nitrobenzene

Many have special names for historical reasons:

CH3 CHO OH

Toluene Benzaldehyde Phenol

(methylbenzene) (phenylmethanal) (hydroxybenzene)
NH2 COOH

Aniline
(aminobenzene) Benzoic acid
2. When 2 substituents are present, their position is
indicated by the prefixes ortho,meta or para or by
the use of numbers.
Cl
Br 1
6 2
1
6 Br
1,2-dibromobenzene 3
2 5
or 4
5
3 o-dibromobenzene
4 Cl
1,4-dichlorobenzene
CH3 or
1 1,3-dimethylbenzene p-dichlorobenzene
6 2 or
5 3 m-dimethylbenzene
4 CH3
 OH
1
6 4-nitrophenol
2
or
5 3
p-nitrophenol
4
NO2

CH3 COOH
1 1
H3C 6
6 2 2
3 5
5 4
3 Br
4
3-bromomethylbenzene 2-methylbenzoic acid
or or
m-bromotoluene o-methylbenzoic acid
3.When three or more groups are on the benzene ring,
a numbering system must be used to locate them.
CH3 OH
1 1
6 NO2 6 Br
2 2
5 3 5 3
4 4
NO2 NO2
2,4-dinitromethylbenzene 2-bromo-4-nitrophenol
or
2,4-dinitrotoulene

COOH
1
6
3,5-dihidroxybenzoic acid
2
5 3
HO 4 OH
4. When benzene ring is attached to a carbon chain
containing other functional group,the benzene ring is
named as a substituent.

1 2 3 4
CH2CH=CHCH3 C6H5 -, phenyl

1-phenylbut-2-ene

CH2Cl C6H5CH2- benzyl

benzyl chloride
 PROPERTIES OF BENZENE
Physical Properties
Benzene is a colourless, volatile, highly flammable and
non-polar liquid.
Its physical properties include:

Molecular 78.11
weight
Melting point 5C
Boiling point 80.1C
Solubility Slightly soluble in water
Very soluble in organic
solvents and oil
Preparation of Benzene
Reaction of Benzene
 1. Halogenation
 The reaction occurs in the presence of Lewis acid
catalyst such as Fe, FeX3,AlX3 ( X is Cl or Br)
The catalyst polarized the halogen molecule & acts as
an electrophile
X

+ X2 Fe or FeX3

EXAMPLE: Bromination rxn

Br

+ Br2 FeBr3
2. Nitration

 Reagents used for nitration of benzene are conc.

nitric acid and conc. sulphuric acid as catalyst.
 The rxn mixture is heated to yield nitrobenzene.

NO2
H2SO4 (conc.) + H2O
+ HNO3
heat
3. Friedel-Crafts Alkylation

This rxn used Lewis acid as a catalyst…such as AlCl3.

R

AlX3
+ RX + HX

Benzene Alkyl halides Alkylbenzene

EXAMPLE:
CH2CH3

+ CH3CH2Cl AlCl3
+ HCl
Benzene Chloroetane
Ethylbenzene
 4. Friedel-Crafts Acylation
 Introducing acyl group R C

O
 Two common acyl groups are the acetyl group and the
benzoyl group

O O
CH3C C
acetyl group
(ethanoyl group) Benzoyl group

 In the presence of anhydrous aluminium chloride, benzene

react with acyl group to form ketone.
For example:

O O
AlCl 3
+ CH3C Cl 80C CCH3 + HCl
acetyl chloride
ketone
 Effect of substituents group on the
benzene ring

1. A substituted group that is already present will have

the following effects on the subsequent substitutions
on the ring.

 Change the reactivity of benzene ring @ rate of rxn

 The orientation of the incoming substituents.

 Group that effect the reactivity
of benzene ring
1. Activating group
G
is the electron donating group
that cause the ring to be more
reactive than benzene.

2. Deactivating group
G
is the electron withdrawing group
that cause the ring to be less
reactive than benzene.
Group that effect the orientation

1. Ortho-para director

The group that directs an electrophile to

the ortho-para position.

2. Meta director

The group that directs an electrophile to

the meta position
 Ortho-para
Groups Meta director
director
-NH2, -NHR,
-NR2,
Activating
-OH, -OR,
C6H5-, R-
-NO2, -COOH, -CN,
Deactivating Halogen -COOR, -SO3H,
-CHO, -COR
EXAMPLE:
What is the products of the rxn if these given
Compound goes nitration process?
CH3 CH3
CH3 NHO3 / H2SO4 NO2
heat and
methylbenzene
Ortho-para director NO2

NO2
NO2 NHO3 / H2SO4
heat NO2
nitrobenzene
meta director
 ADDITIONAL PROBLEMS
1. Write structural formulas for each of the following;
CH3 Br OH
Br

O 2N NO 2

Br o-dibromobenzene 3,5-dinitrophenol
p-bromotuluene

CH2Br H3C CH3

C
CH3

Benzyl bromide
tert-buthylbenzene