4.

AROMATIC HYDROCARBONS

The term aromatic (Greek; aroma means fragrance) was first used for compounds having
pleasant odour although the structure was not known. Now the term aromatic is used for a class
of compounds having a characteristic stability despite having unsaturation. These may have
one or more benzene rings (benzenoid) or may not have benzene ring (non-benzenoid).
Benzenoid compounds include benzene and its derivatives having aliphatic side chains (arenes)
or polynuclear hydrocarbons, eg. naphthalene, anthracene, biphenyl etc.

Benzene
CH
3
CH
CH
3
C H
3
N
H
Pyrrole
Isopropyl benzene
(Cumene)
Toluene


Structure of Benzene

Benzene has been known since 1825 when it was first isolated by Michel Faraday. Form
elemental analysis and molecular mass determination, it was found that the molecular formula
of benzene is C
6
H
6
indicating high unsaturation. However, benzene does undergo addition
reactions in contrast to unsaturated hydrocarbons, although it mainly undergoes substitution
reactions.

In 1865 Friedrich August Kekule proposed a ring structure for benzene (I). However, many
alternative structures have been proposed from time to time by different workers. (II-IV).
Kekule
(I)
Dewar
(II)
Claus
(III)
Baeyer
(IV)


Then main objection against Kekule structure was that it should yield two ortho disubstituted
products when it reacts with bromine. However, experimentally benzene was found to yield
only one product.

Kekule removed this objection by proposing that the double bonds in benzene are continuously
oscillating back and forth between two adjacent positions. Since positions of double bonds are
not fixed, only one product is formed. This structure came to be known as Kekules dynamic
formula, which formed the basis for the present electronic structure of benzene.

Modern Concept

Stability of Benzene (Resonance)

Benzene resists addition whereas it readily undergoes substitution reactions, like nitration,
halogenation etc. This indicates that benzene is more stable than the hypothetical
cyclohexatriene molecule. This has been proved by the fact that the enthalpies of
hydrogenation and combustion of benzene are lower than expected. Enthalpy of hydrogenation
is the change in enthalpy when one mole of an unsaturated compound is hydrogenated. It has
been found experimentally that enthalpy of hydrogenation for disubstituted alkenes, R-
CH=CH-R varies between 117-125 kJ mol
1
. Accordingly, the values for cyclohexene and
cyclohexa-1, 3-diene and hypothetical cyclohexa-1, 3, 5-triene were calculated compared with
their experimental values.

While the experimental values of enthalpy of hydrogenation for cyclohexene is similar to the
value expected, the variation in the case of cyclohexa-1, 3-diene is small and is due to
delocalization. The expected value of enthalpy of hydrogenation of benzene is much higher
than the corresponding calculated value for hypothetical cyclohexa-1, 3, 5-triene indicating
that benzene does not have this type of structure.

X-ray studies show that it is planar molecule and that all six CC bonds in benzene are of
equal length (139 pm), intermediate between CC single bond (154 pm) and C=C (134 pm).
All six carbons are sp
2
hybridized and all bond angles are 120
o
. Benzene is a hybrid of various
resonating structures, the two Kekule structures A and B, being the main contributing forms.
A
B
H H
H H
H H
Kekule Structures
120
o
139 pm


Aromaticity in Benzene and Related Systems
After the structure of benzene was established, the term aromatic was adapted for such
compounds which despite having t bonds (unsaturation) resist addition and instead undergo
substitution. The aromaticity in benzene is attributed to the six delocalized pi electrons in the
coplanar carbon hexagon. When a bonding orbital is not restricted to two atoms but is spread
over more than two atoms, e.g. six in benzene, such bonding orbitals are said to be delocalized.
Delocalisation results in greater stability.
The modern theory of aromaticity was advanced by Eric Huckel 1931. Aromaticity is a
function of electronic structure. Any polynuclear compound, heterocyclic rings or cyclic ions
may be aromatic if these have a specific electronic structure. The important features of the
theory are

1. Delocalization:
Complete delocalization of t electron cloud of the ring system is a necessary requirement
for aromatic character.
2. Planarity:
Complete delocalization of t-electron cloud is possible only if the ring is planar. This is the
reason that benzene is aromatic but cyclooctatetraene is not, since the latter is not a planar
molecule.

Huckels rule or (4n + 2) electron rule:
The rule states that in a conjugated, planar, cyclic system if the number of delocalized t-
electrons is (4n + 2) where n is an integer, i.e., 1, 2, 3 etc. Benzene, naphthalene, anthracene
and phenanthrene are aromatic as they contain (4n + 2)t electrons i.e. 6, 10, 14, t electrons in
a conjugated cyclic system. The cyclopentadiene and cyclooctatetraene are non-aromatic as
instead of (4n + 2)t e

these have 4n t e

. Moreover, they are non-planar.

Naphthalene
10 electrons
n = 2
t
Benzene
6 electrons
n = 1
Anthracene
14 electrons
n = 3
t
t

Cyclopentadiene
Non-aromatic cyclic hydrocarbons
Cyclooctatetraene
4 e

t 8 e

t


Benzene was first isolated by Faraday from cylinders of compressed illuminating gas obtained
from the pyrolysis of whale oil.
Benzene was first synthesised by Berthelot by passing acetylene through a red hot tube.

red hot tube
2 2 6 6
3C H C H
In the laboratory it was first prepared by heating benzoic acid or phthalic acid with calcium
oxide.
COOH
CaO

COOH
COOH
benzoic acid
phthalic acid

PROPERTIES
(i) It is a colourless liquid with boiling point of
o
80 C.
(ii) It is inflammable, burning with a smoky flame due to high carbon content.
(iii)It is slowly attacked by acid permanganate to form
2 2
CO and H O.

6 6 2 2
C H 15[O] 6CO 3H O + +

(iv)
Ni
2
3H +
Cyclohexane

(v)
Cl
Cl
Cl Cl
Cl
Cl
sunlight
2
3Cl +
Benzene hexachloride


Ex. 14. Using Huckels rule predict, which of the following hydrocarbons will exhibit aromatic
stabilization?
(a)

(b)

(c)

(d)

Sol. Only (a) troplyium cation with 6t electrons.

..................


Ex.15. Which is more stable?
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
or
C H
3
CH
3
C H
3
CH
3

Sol. (I) is more stable

Reaction of benzene:
Major reactions of benzene ring are electrophilic substitution reactions.

SO
3
H
3 2 4
SO / H SO

2 3
Br / FeBr

COCl
3
2 4
HNO
H SO

NO
2
3
RCOCl / AlCl

2 3
Cl / FeCl

Cl
Br
3
RCl / AlCl

R
2 3
I / HNO

I



MECHANISM OF ELECTROPHILIC SUBSTITUTION REACTIONS

1. Nitration:
(i) Formation of electrophile
+
2
NO :

3 2 4 2 4 3
HNO 2H SO NO 2HSO H O
+ +
+ + +
(base) (acid) (nitronium ion)

(ii) Electrophilic attack by
+
2
NO :

slow
2
NO
+
+
H
NO
2
NO
2
H
NO
2
H
NO
2
H

In the intermediate, attacked carbon atom changes its state of hybridization from trigonal to
tetrahedral.

2
Rate K[substrate] [NO ]
+
=
(iii)Loss of proton :

NO
2
fast

NO
2
H
H
+
+

2. Friedel Craft Alkylation:
This reaction involves the introduction of alkyl group into benzene ring in presence of catalyst.
The alkylating agent may be R X, ROH or alkene. The catalyst is a Lewis acid,
3 3
BF , AlCl ,
2 4
H SO or
3 4
H PO .

CH
3
3
3
CH Cl
AlCl

CH
CH
3
CH
3
2 4
H SO
3 2
CH CH CH + =




Mechanism:
Step I: Formation of electrophile (carbonium ion) stability order of carbonium ion is

o o o
3 2 1 > > with RX
3 4
RCl AlCl R AlCl

+ +




2 4 2
R OH H (from H SO ) R H O
+
+ +



With ROH:

2 4 2
ROH H (from H SO ) R H O
+
+ +



With alkene :

2 3
RCH CH H RCHCH (markovnikov' s rule)

+
= +
Step II :

slow
R

+
R
H

Step III :

fast

R
R
H
H
+
+

Examples:

3
AlCl
3 2 2
(CH ) CHCH Cl +
C(CH
3
)
3
major


CH
3
C
CH
3
CH
3
is more stable than CH
3
CHCH
2
CH
3
o
(1 )
o
(3 )

or
o
3 2 3
CH CHCH CH (2 )

carbonium ion.
This is an example of intermolecular Friedel Craft alkylation. But if the side chain contains
four or five carbons with halogen at the end then it may undergo intramolecular Friedel
Craft reaction.

3
AlCl

CH
2
CH
2
CH
2
CH
2
Cl
HCl +

3. Friedel Craft Acylation:
Replacement of H
+
of benzene by RCO
+
group using carboxylic acid, esters, acid chloride or
acid anhydride as acylating agent in the presence of Lewis acid.

3
AlCl
3 2
(CH CO) O +
COCH
3
HCl +
3 3
CH COCl / AlCl

COCH
3
3
CH COOH +


Mechanism:
(i)
3 4
RCOCl AlCl RCO AlCl
+
+ +

R C
O
(I)
acylcation
R C
O
(II)

(II) is more stable than (I) because each atom has a complete octet.
(ii)
slow
RCO

+
COR
H

(iii) COR
fast
H
+

COR
H

Examples:

CH
2
CH
2
CH
2
COOH
3 4
H PO

O

Reactions of side chains
1. Halogenation:
R

With
2
X in presence of
3
FeX undergoes electrophilic substitution at o-
and p- position and in the absence of
3
FeX and in the presence
of light or high temperature undergoes substitution in the side
chain (free radical substitution).

CH
3
2
Cl
heat

2
Cl heat or light

CH
3
Cl
CH
3
Cl
CH
2
Cl
2 3
Cl / FeCl

CHCl
2
2
Cl
heat

CCl
3