Aromatic Hydrocarbons

(Chapter 32)
Aromatic Hydrocarbons
Aroma

Ring of sp2 carbon atoms

(4n+2) π delocalized bonding electrons

CH3

Benzene Methylbenzene Napthalene

Discovery of the structure of
benzene
Molecular Formula: C6H6
Structural Formula: ?

Possible structure:
A CH2=CH-C≡C-CH=CH2
B CH3-C≡C-C≡C-CH3

A is ruled out because only ONE

monosubstituted chlorobenzene.
Discovery of the structure of
benzene

Evidence: There are THREE disubstituted

isomers of C6H4Cl2.

B (CH3-C≡C-C≡C-CH3 )is ruled out too!

 Discovery of the structure of
benzene
Kekule(1865): Chemist and Dreamer

…… one of the snakes has seized hold

of its own tail …….

Cl Cl
H Cl
H C H
C C Cl
C C
H C H Cl
Cl
H
Discovery of the structure of
benzene

Objections to Kekule Benzene:

•A 4th isomer of C6H4Cl2

•Surprising stability of benzene
•All the C-C bonds are the same length
 Discovery of the structure of
benzene
Delocalization of Bonding
Electrons

•3e- in sp2 hybrids form

normal covalent bonds
•4th e-, one from each carbon
atoms are free to visit
all the atoms on the ring Delocalized π-bond system
(delocalized bonding
electrons)
 Stability of the Benzene Ring
Enthalpy
kJ/mol Resonance
Energy
150.4
-358.8
-208.4
Cyclohexane

Reaction co-ordinate
 Reactions of Benzene

•No reaction with Br2/dark

•No reaction with MnO4-/H+

Benzene

Although benzene is unsaturated,

it is resistant to oxidation and addition reaction
because of the energy of delocalization is lost
in such reaction.
 Electrophilic Aromatic
Substitution
General Mechanism:
•Formation of Electrophile, E+
•Attack of E+ on π electron cloud of benzene
•Loss of a proton

r.d.s H -H+
E+ E
E
+
 Benzenonium ion

+
H H H
+
E E E
+

H
OR +
E

sp3
 Electrophilic Aromatic
Substitution

H
H
E
+

+ E+
E
+H+

Reaction coordinate
 Electrophilic Aromatic
Substitution

Reaction Reagent Catalyst Product E+ or E

Halogenation X2(Cl,Br) FeX3 ArCl, ArBr X+

Nitration HNO3 H2SO4 ArNO2 NO2

+

Sulphonation H2SO4 None ArSO3H SO3

Alkylation RX(Cl,Br) AlX3 Ar-R R+

 Formation of E+

• X2 + FeX3 => X+ + FeX4-

• H2SO4 + HONO2 => HSO4- + H2O+NO2 =>
H2O + +NO2
• 2H2SO4 => HSO4- + H3O+ + SO3
• RX + AlX3 => R+ + AlX4-
Reversible nature of sulphonation

SO3H
c.H2SO4
80oC, reflux
Benzenesulphonic acid

SO3H
H2O, H2SO4 + H2SO4
T>100oC
 Eact ≈ Eact*

H
H
SO3-
+

+ SO3
SO3-
+H+

Reaction coordinate

k-1 H k2
ArH + SO3  Ar+ - → ArSO3 + H k-1 ≈ k2
- +
k1 SO3
Oxidation of alkylbenzene
CH3 COO- COOH

KMnO4/OH- H3O+
heat

KMnO4/OH- is better than KMnO4/H+

As C6H5COO- acts as a solvent that mix
C6H5CH3 and MnO4-
 Oxidation of alkylbenzene
Oxidation takes place at first by the abstraction
of a phenylmethyl hydrogen by the O.A., once
take place, oxidation continues until a
carboxyl group is left.
CH2CH2CH2R COOH

CR3
No reaction (no H on C)