AROMATIC HYDROCARBONS

Organic compounds are divided into two main classes: the aliphatic and the aromatic.

The molecules of both saturated and unsaturated aliphatic compounds are open-chain
(acyclic) or simple rings (cyclic) structures.

The term aromatic refers to a major class of unsaturated cyclic organic compounds which
includes benzene and its derivatives. Benzene is an unsaturated, but highly stable, cyclic
molecule containing six carbon atoms. Aromatic hydrocarbons are hydrocarbons which
have benzene ring in their structures. They are sometimes called arenes.

These hydrocarbons are also known as ‘arenes’. Since most of them possess pleasant odour
(Greek; aroma means pleasant smelling), the class of compounds was named as ‘aromatic
compounds’. The parent member of the family is benzene having the molecular formula
C6H6. it has hexagonal ring of six carbon atoms with three double bond in alternate position.

Aromatic compounds containing benzene ring are known as benzenoids and those not
containing a benzene ring are known as non-benzenoids.

For eg:

STRUCTURE AND SHAPE OF THE BENZENE C6H6 MOLECULE :

Resonance Structure Of Benzene
The stability of benzene can be explained on the basis of concept of resonance. Kekule
in1865 gave a ring structure for benzene in which the positions of the three double bonds are
not fixed. He suggested that the double bond keep on changing their positions an this is called
Resonance. The resonance structure of benzene is supported by the following facts:
1. The carbon-carbon bond length in benzene is 139 pm which is intermediate between
bond lengths for C-C bond (154 pm)and C=C bond (134 pm) and the value is the
same for all the bonds.
2. Due to resonance the -electron charge in benzene gets distributed over greater area
i.e., it gets delocalised. As a result of delocalisation the energy of the resonance hybrid
decreases as compared to contributing structure by about 50kJ mol-1. the decrease in
energy is called resonance energy. Therefore, it is stabilised and behaves as a
saturated hydrocarbon.
3. If the positions of double bonds are fixed. We expect two isomers of 1,2-
dichlorobenzene as shown below (one having Cl atoms attached to C-C bond and the
other having Cl atoms attached to C=C bond).

According to the orbital concept, each carbon atom in benzene is sp2- hybridised and one
orbital remains unhybridised. Out of the three hybrid orbitals, two overlap axially with the
orbitals of the neighbouring carbon atoms on both side to form σ-bond. The third hybridised
orbital of the carbon atom overlaps with the half-filled orbital of the hydrogen atom resulting
in C-H bonds. Thus, benzene has a planar structure –with bond angle of120˚ each.

There is still one unhybridised 2p-orbital left on each carbon atom. Each one of these orbitals
can overlap sidewise with similar orbital of the carbon atoms on either sides to form two sets
of -bonds.

The resultant -orbital cloud is spread over all the six carbon atoms (shown in fig c.). As a
result, there are two continuous rings of -electron clouds, one above and the other below
the plane of the carbon atoms(shown in fig d.).
c)

d)

electron cloud

1.22 Aromaticity
Aromatic compounds are those which resembles benzene in chemical behaviour. These
compounds contain alternate double and single bonds in a cyclic structure. They undergo
substitution reaction rather than addition reaction. This characteristic be behaviour is called
aromaticity. The aromaticity depends upon the electronic structure of the molecule.

The main essential for aromaticity are:

 Delocalisation: the molecule should contain a cyclic cloud of delocalized  electron
above and below the plane of the molecule
 Planarity: for the delocalisation of -electron the ring must be planar to allow cyclic
overlap of p-orbitals. Therefore, for a molecule to be aromatic, the ring must be planar.
 (4n+2) electron: for aromaticity, the -electron could must contain a total of (4n+2)
electrons where n is an integer equal to 0,1,2,3……..n . This is known as Huckel Rule.
 Benzene, 6  e- Naphthalene, 10  e- Anthracene, 14  e-
(n=1) (n=2) (n=3)

PREPARATION OF BENZENE

 Decarboxylation of aromatic acid

benzene is prepared in the laboratory by heating sodium benzoate with soda lime.

 Reduction of phenol
Benzene can be prepared from phenol by distillation with zinc.

PROPERTIES OF BENZENE

PHYSICAL PROPERTIES
 Benzene and its homologues containing up to eight carbon atoms are colourless liquids
with characteristic smell.
 Aromatic hydrocarbons are immiscible with water but are soluble in organic solvents.
 They are inflammable and burn with sooty flame.
 They are toxic and carcinogenic in nature.
 The melting and boiling point of aromatic hydrocarbon increase with increasing
molecular mass. This is due to increase in magnitude of van der Waals’ forces of
attraction with increase in molecular size. Amongst isomeric arenes, (i.e., o-,m- and p-
xylenes), the p- isomer has the highest melting point because it is most symmetrical.

CHEMICAL PROPERTIES

A. ELECTROPHILIC SUBSTITUTION REACTION

i)Nitration

The replacement of a hydrogen atom in the ring by a nitro (-NO2) group is called nitration. It
is carried out by heating benzene with the nitrating mixture consisting of concentrated nitric
acid and sulphuric acid to about 330K.

ii) Halogenation

The replacement of a hydrogen atom in the ring by a halogen atom (F, Cl, Br or I) is called
halogenation. Arenes react with halogen in the presence of a Lewis acid like anhydrous
FeCl3, FeBr3 or AlCl3 to yield haloarenes.
iii)Sulphonation

The replacement of a hydrogen atom in the ring by a sulphonic acid (-SO3H) group is called
sulphonation. It is carried out by heating benzene with fuming sulphuric acid and oleum.

iv)Friedel-Crafts Alkylation

When benzene is treated with an alkyl halide in the presence of anhydrous aluminium
chloride, alkylbenene is formed.

v) Friedel-Crafts Acylation

The reaction of benzene with acyl halide or acid anhydride in the presence of lewis acid
(AlCl3) Yields acyl benzene

Mechanism of electrophilic substitution reaction

According to experimental evidences, SE (S= substitution; E= electrophilic) reaction are
supposed to proceed via the following three steps:
a)Generation of the electrophile.
b)Formation of carbocation intermediate.
c)Removal of proton from the carbonation intermediate.

Step 1: Generation of electrophile

The attacking reagent may not be strong electrophile. Therefore, first of all an electrophile is
generated by some preliminary reaction. For example , during chlorination of benzene, an
electrophile (Cl +) is generated by reacting with anhydrous AlCl3 used as catalyst.

Cl2 + AlCl3 Cl+ + AlClˉ4

Step 2:Formation of Carbocation ( arenium ion)

The electrophile E+ approaches the -electron cloud of the aromatic ring and forms a bond
with carbon, creating a positive charge on the ring. This results in the formation of a sigma
complex (called arenium ion).

The arenium ion gets stabilized by resonance

The resulting carbocation has three important contributing structures which spread the
positive charge over the remaining carbon atom.
Step 3: Removal of Proton

The carbocation formed loses a proton to the nucleophile (Nuˉ) present in the reaction
mixture to form a substitution product. During this step, the aromatic character of the benzene
ring is restored and this step is fast.

The loss of proton allows the two electrons from the carbon-hydrogen bond to move to
regenerate the aromatic ring and thus restoring the aromatic character.

B. ADDITION REACTION

1)Addition of Hydrogen
Benzene reacts with hydrogen in the presence of a catalyst such as nickel, or platinum at 473
to 573 K under pressure to form cyclohexane.

2) Addition of Halogen

Benzene reacts with chlorine or bromine in the presence of sunlight and absence of halogen
carrier to form benzene hexachloride.
3) Combustion

On completely burning with oxygen, benzene gives carbon dioxide and water with the
evolution of a large amount of energy.

Directive influence of a functional group in monosubstituted benzene

When monosubstituted benzene is subjected to further substitution, three possible

disubstituted products are not formed in equal amounts. Two types of behaviour are observed.
Either ortho and para products or meta product is predominantly formed. This behaviour
depends on the nature of the substituent already present in the benzene ring and not on the
nature of the entering group. This is known as directive influence of substituents.

a)Ortho and para directing groups

b)Meta directing group

a) Ortho and para directing group

The groups which direct the incoming group to ortho and para position are called ortho and
para directing groups. As an example, let us discuss the directive influence of –OH (phenolic)
group.
The resonance structures of phenol show that the overall electron density on the benzene ring
increases in comparison to benzene. Therefore, it is an activating group.

b) Meta directing groups

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, -COR, -COOH, -
COOR, -SO3H, etc. Let us take an example of Nitro group.

Nitro group reduces the electron density in the benzene ring due to its strong-I effect.
Nitrobenzene is the resonance hybrid of the following structures.

Carcinogenicity and toxicity

Benzene and polynuclear hydrocarbon containing more than two benzene rings fused
together are toxic and said to possess cancer producing (Carcinogenic) property. Such
polynuclear hydrocarbons are formed on incomplete combustion of organic materials like
tobacco, coal and petroleum. They enter into human body and undergo various biochemical
reaction and finally damage DNA and cause cancer.