AROMATIC HYDROCARBON ( also known as ‘arenes’)

• Aromatic compounds containing benzene ring are known as

benzenoids and those not containing a benzene ring are known as
non-benzenoids.
Structure of Benzene

August Kekulé Structure for Benzene

Cyclic arrangement of six carbon atoms with alternate single and double
bonds and one hydrogen atom attached to each carbon atom.
Benzene is a hybrid of various resonating structures.
Aromaticity

A compound is Aromatic if it has following characteristics

(i) Planarity

(ii) Complete delocalisation of the pi electrons in the ring

(iii) Presence of (4n + 2) pi electrons in the ring where n is an integer (n =

0, 1, 2, . . .).

This is often referred to as Hückel Rule.

Identify the aromatic compound from the following:-

1. Benzene has 6 ∏ electrons. ( 3 double bonds)

i.e.: ( 4x1+2) ∏ electrons
Obeys Huckel rule of having ( 4n+2) ∏ electrons .
∴ Aromatic compound
4n+2 =6 , n= 4/4 =1

2. Has 10 ∏ electrons (5 double bonds)

i.e.: ( 4x2+2) ∏ electrons
Obeys Huckel rule of having ( 4n+2) ∏ electrons

∴ Aromatic compound
 3. Cyclopentadiene
Has 4 ∏ electrons (2 double bonds)
Does not Obey Huckel rule of having ( 4n+2) ∏ electrons

∴ Not an Aromatic compound.

4. Has 6 ∏ electrons. ( 2 double bonds + 2 electrons)
i.e.: ( 4x1+2) ∏ electrons
Obeys Huckel rule of having ( 4n+2) ∏ electrons
∴ Aromatic compound
Homework
Predict whether the following compounds are aromatic
a) Anthracene b) Phenanthrene c) Cycloheptatrienyl cation
 Preparation of Benzene
(i)Cyclic polymerisation of ethyne

(ii)Decarboxylation of aromatic acids

Sodium salt of benzoic acid on heating with sodalime gives
benzene.
iii) Reduction of phenol: Phenol is reduced to benzene by
(

passing its vapours over heated zinc dust

 Physical properties
 Aromatic hydrocarbons are non- polar molecules
 colourless liquids or solids with a characteristic aroma
 immiscible with water but are readily miscible with organic
solvents.
 burn with sooty flame

Chemical properties
 Arenes are characterised by electrophilic substitution reactions.
 They also undergo addition and oxidation reactions.
 1) Electrophilic substitution reactions
The common electrophilic substitution reactions of arenes are
 nitration
 halogenation
 sulphonation
 Friedel Craft’s alkylation
 Friedel Craft’s acylation
 In all these attacking reagent is an electrophile (E+)
(i)Nitration:
A nitro group (NO₂) is introduced into benzene ring when benzene is heated
with a mixture of concentrated nitric acid and concentrated sulphuric acid
(nitrating mixture).

Q)Convert benzene to nitrobenzene.

(ii) Halogenation: Arenes react with halogens in the presence of a Lewis
acid like anhydrous FeCl3, FeBr3 or AlCl3 to yield haloarenes

Q) Convert benzene to chlorobenzene

Q) Convert benzene to bromobenzene
iii) Sulphonation: The replacement of a hydrogen atom by a sulphonic acid

group in a ring is called sulphonation. It is carried outby heating benzene with

fuming sulphuric acid (Oleum).

 iv) Friedel-Crafts alkylation reaction:

When benzene is treated with an alkyl halide in the presence of anhydrous

aluminium chloride, alkylbenzene is formed .

Q) Convert benzene to toluene

v) Friedel-Crafts acylation reaction:
When benzene is treated with an acyl halide in the presence of
anhydrous aluminium chloride, acylbenzene is formed.
 (vi) With excess of electrophilic reagent
 Further substitution reaction may take place by replacing more hydrogen
atoms of benzene ring by the electrophile.
 Benzene on treatment with excess of chlorine in the presence of
anhydrous AlCl3 can be chlorinated to hexachlorobenzene (C6Cl6)
 2)Addition reactions:-
i) Under vigorous conditions ( at high temperature and/or pressure in
the presence of Ni catalyst) hydrogenation of benzene gives
Cyclohexane

ii) Under ultra-violet light, three chlorine molecules add to benzene to produce

Benzene hexachloride, C6H6Cl6 which is also called gammaxane.

Q) How is BHC different from hexachlorobenzene
Ans: BHC is formed by the addition reaction of benzene
and chlorine , whereas hexachlorobenzene is formed by the
substitution reaction.

3) Combustion
When heated in air, benzene burns with sooty flame
producing CO2 and H2O.
Directive influence of a functional group in mono
substituted Benzene
• When mono substituted, Benzene is subjected to further substitution,
three di substituted products are possible, but they are not formed in
equal amounts.
• Either ortho and para products or meta product is predominantly formed.
• This depends on the nature of the substituent already present in the
benzene ring
This is known as directive influence of substituents.
Ortho and para directing groups:

The groups which direct the incoming group to ortho, and para positions
are called ortho and para directing groups.
Eg:- directive influence of phenolic (–OH) group.
• The electron density is more on o – and p – positions. Hence,
the substitution takes place mainly at these positions.
• The overall electron density increases at these positions of
the ring due to resonance.
• – OH group activates the benzene ring for the attack by an
electrophile.
• Other activating groups are –NH2, – CH3, – C2H5, etc.
Meta directing group:
The groups which direct the incoming group to meta position are called
meta directing groups.
Some examples of meta directing groups are –NO2, –CN, –CHO, –COOH etc.
• The overall electron density on benzene ring decreases making
further substitution difficult.
• These groups are also called ‘deactivating groups. The electron
density on o– and p– position is comparatively less than that at
meta position. Hence, the electrophile attacks on comparatively
electron rich meta position resulting in meta substitution.
 CARCINOGENICITY AND TOXICITY
 Benzene and polynuclear hydrocarbons containing more than
two benzene rings fused together are toxic and possess
carcinogenic property.
 They are formed on incomplete combustion of organic materials
like tobacco, coal and petroleum.
 They damage DNA and cause cancer .
Revision Worksheet
1. Covert:
a) Ethene to 1,2-dibromoethane
b) Ethene to ethanol
c) Propyne to propanol
d) Benzene to toluene
e) 1- Bromopropane to 2-Bromopropane
f) Ethyne to toluene
2. What happens when benzene is treated with
g) Excess chlorine in presence of anhydrous AlCl 3 in dark.
h) Hydrogen at high temperature and pressure in presence of nickel catalyst.
i) Chlorine in presence of UV light.
3. An alkene on ozonolysis gave Propanal and Propanone. Identify the alkene
and write its IUPAC name.