AROMATICITY OF BENZENOID COMPONENTS

The meaning of the word aromaticity has evolved as understanding of the reason for the
special properties of benzene and other aromatic molecules. Originally, aromaticity was
associated with a special chemical reactivity. In the nineteen century it was recognized that
the aromatic compounds differ greatly from unsaturated aliphatic compounds. The aromatic
hydrocarbons were considered to be those unsaturated systems that underwent substitution
reactions in preference to addition. In 1925, Armit and Robinson recognized that the aromatic
properties of benzene ring are related to the presence of closed loop of electrons, the aromatic
sextet. Later, it was recognized that a major contribution to the stability of aromatic system is
due to the delocalization of the electrons in the system. Currently, aromaticity is usually
described in molecular orbital (MO) terminology.

Huckel’s rule- application to Benzenoid and non-benzenoid compounds

A simple expression of the relationship between a molecular orbital description of a structure

and aromaticity is known as the Huckel rule. According to Huckel rule ‘Planar monocyclic

completely conjugated hydrocarbons will be aromatic when the ring contains (4n+2)

electrons’. n=0,1,2,3 etc.,

Huckel’s rule predicts aromaticity for both benzenoid and non benzenoid
compounds a. Benzenoid compounds
Compounds containing one or more benzene rings are known as benzenoid compounds

1. Benzene

Number of bonds = 3

Number of electrons = 6

According to Huckel rule, when n=1, (4n+2) = (4 X 1 +2) = 6

electrons Hence number of electrons in the compound must be equal to 6

Since Benzene contains 6 electrons, it is aromatic.

2. Naphthalene

Number of bonds = 5 Number of

electrons = 10

According to Huckel rule, when n=2, (4n+2) = (4 X 2 +2) = 10 electrons

Hence number of electrons in the compound must be equal to 10

Since naphthalene contains 10 electrons, it is aromatic.