AROMATIC

HYDROCARBONS
Aromatic was used to describe fragrant
substances such as benzene (from coal
distillate), benzaldehyde (from cherries,
peaches, and almonds), and toluene (from tolu
balsam).
It was soon realized, however, that substances
classed as aromatic differed from most other
organic compounds in their chemical behavior.

Aromatic - refers to the class of compounds that

contain six-membered benzene-like rings with
three double bonds.
Many valuable compounds are aromatic in part,
such as the steroidal hormone estrone and the
cholesterol lowering drug atorvastatin,
marketed as Lipitor
 Benzene Discovery
Michael Faraday (1825)
– isolated the new hydrocarbon from an
illuminating gas which he called “bicarburet of
hydrogen”.
- determined C:H ratio to be 1:1
Eilhard Mitscherlich (1834)
- determined molecular formula to be C6H6
- prepared the same substance by heating
benzoic acid with lime.
C6H5CO2H + CaO  C6H6 + CaCO3
Eventually, because of its relationship to benzoic
acid, this hydrocarbon came to be named
benzin, then later benzene, the name by which
it is known today.
Other related compounds with low C:H ratios
had a pleasant smell, so they were classified as
aromatic.
Benzene derived products are well known to be
pleasantly fragrant.
Although benzene and toluene are not
particularly fragrant compounds themselves,
their origins in aromatic plant extracts led them
and compounds related to them to be classified
as aromatic hydrocarbons
August W. von Hofmann (1845)
- prepared benzene from coal tar – primary
source for the industrial production of benzene
Kekulé and the Structure of Benzene
August Kekulé (1866)
- used the principles of structural theory to postulate a
structure for the benzene molecule.
Kekulé based his postulation on the following premises:
• The molecular formula for benzene is C6H6.
• All the carbons have four bonds as predicted by
structural theory.
• All the hydrogens are equivalent, meaning they are
indistinguishable from each other.
Kekule suggested a ring structure for benzene
which consisted of a cyclic planar structure of six
carbons having alternate double and single
bonds. Each of the six carbons was attached to
one hydrogen.
 Resonance

Benzene have the same arrangement of atoms,

but differ in the placement of electrons. Thus
they are resonance forms.
Benzene is often represented by a hexagon
containing an inscribed circle. The circle
represents the movement of the electrons
throughout the entire molecule.
Sir Robert Robinson – suggested the circle-in-a-
hexagon symbol to represent what he called the
“aromatic sextet” – the six delocalized 𝛑
electrons of the three double bonds.
Structure of Benzene
- Has eight fewer hydrogens than the corresponding six
carbon alkane (C6H14) and is clearly unsaturated,
usually being represented as a six-membered ring with
alternating double and single bond.
- Structure is planar, hexagonal.
- All C–C–C bond angles are 120°.
- Each C is sp2-hybridized and has a p orbital
perpendicular to the plane of the six-membered ring
The Criteria for Aromaticity—Hückel’s Rule
1. A molecule must be cyclic.
• To be aromatic, each p orbital must overlap
with p orbitals on adjacent atoms.

2. A molecule must be planar.

• All adjacent p orbitals must be aligned so that
the π electron density can be delocalized.
3. A molecule must be completely conjugated.
• Aromatic compounds must have a p orbital on every
atom.

4. A molecule must satisfy Hückel’s rule, and contain a

particular number of π electrons.
Structural Formulas of Aromatic Compounds
Considering aromaticity, a compound can be classified
in one of three ways:
Aromatic—A cyclic, planar, completely conjugated
compound with 4n + 2 π electrons.
 Sources of Aromatic Hydrocarbons
1. Coal.
High temperature distillation of coal tar. Coal is a mixture
of benzene-like rings joined together. Under high
temperature, it produces coal tar which, upon fractional
distillation, such as benzene, toluene, xylene, indene,
naphthalene, biphenyl, anthracene and phenanthrene.

2.Petroleum.
Heating petroleum at high temperature under high
pressure over a catalyst. Petroleum consists mainly of
alkanes which, at high temperature under pressure over a
catalyst, convert into aromatic compounds.