AROMATICITY

Aliphatic compound

Open chain compounds Cyclic compounds

Aromatic compounds:

Compounds that resemble benzene in chemical behaviours.

Structure of Benzene:

a) Molecular formula: C6H6

• In 1858 August Kekule proposed C-atoms can join to form

chains.

• In 1865 – he proposed the closed ring system of carbon chains.

CH CH CH
HC
CH CH CH CH
C CH2 CH3 C C C C CH3
CH
CH CH CH CH CH
CH CH

I II III IV
Kekule Formula Dewar Formula

CH2 CH C C CH CH2

v
 Kekule Structure:
Most satisfactorily accepted.
a) Benzene yield only one mono substitution Products
(C6H5Y).

C6H5Br When one hydrogen atom is replaced

by Br.

E.g: C6H5Cl , C6H5No2

Each hydrogen atom must be equivalent to other hydrogen.

So replacement of any hydrogen yield the same product.
 CH2 CH2 C C C CH2

CH2 CH C C CH CH2 Br

V H3C CH2 C C C CH2

Br

All the hydrogens are not equivalent. In the same way II and III are
not having equivalent hydrogens.

c) Benzene yields three isomeric distribution products.

C6H4Br2 3 C6H4ClNo2 3
Dibromo benzene Chloro nitro benzene

CH3 C C C C be CH
Must rejected
3
•Structure – I is consistent with the fact 3 isomeric dibromo
derivatives -1,2 & 1,3 & 1,4 dibromo compounds.
Br Br Br

C C C
CH C Br CH CH CH CH

CH CH CH C CH CH
CH CH Br C

Br
1,2 - dibromo benzene 1,3 - dibromo benzene 1,4 - dibromo benzene

But kekule visualised benzene molecule as a dynamic thing.

H H

H C H H C H
C C C C

C C C C
H C H H C H

H H
 Br Br

C Br Br C
C C C C

C C C C
C C

For each dibromo derivative, two isomer are possible . But they are
in rapid equilibrium with each other so they are considered as single
structure.

 Defects of Kekule’s Structure:

•It could not explain the inert nature of benzene.

•Two ortho substitution products of benzene were possible.
X X
X X

•This is accounted by the rapid state of oscillation of the double

bonds.
•In 1932, Levine & Cole subjectedo-Xylene to ozonolysis glyoxal,
Methyl glyoxal & Dimethyl glyoxal

CH3

CH3

2 CH3CO.CHO + CHO

CHO

CH3

H3C CH3CO 2 CHO

+

CH3CO CHO

•Closed chain ruptures at the position of the double bonds to yield

these products.
•Some other Formulae:
•Kekule’s formula did not explain the peculiar behaviour of double bonds in benzene.

•Dewar’s formula not symmetrical

•Prism formula no double bonds

X-ray spectrum benzene has a regular hexagonal structure.

In all the future formulae length of some bonds is too much. Therefore it has a
point of weakness rather than strength.

Armstrong-Bayer’s Centric formula – 4th valency-is represented as directed towards the

centre of the ring.
It does not explain the stability of the ring and the behaviour of the polynuclear
hydrocarbons.

Thiele’s Formula:
H
C
HC CH

HC CH
C
H

No difference between 1:2 and 1:6 position. At the same time there being no free
valencies it behaves as a saturated compound.

As suggested by Thiele, if the aromatic character is due to symmetrical conjugation

of the benzene ring then, cyclo octatetrane should also exhibit aromatic character, but
it has a typical aliphatic unsaturated character.
 ORBITAL PICTURE OF BENZENE
 In terms of the molecular orbital theory benzene
spectroscopic studies and X-ray analysis is a regular
flat hexagon (Angle=120◦) with all the six carbon atoms lying
in the same plane and each C-C-H angle also being 120◦.
Each carbon atom sp2 hybridization

Six Sigma C-H bonds

Benzene Six Sigma C-C bonds

Six 2pz Orbitals

(one of each C-atom)
Which are all parallel and perpendicular to the plane of the
ring.
 I II III IV

II & III overlapping of 2pz orbital with

neighbouring p- orbital.

All the six orbital are therefore completely delocalized and

form a molecular orbital embracing all 6 carbon atom (IV).
 H H

C C

H C C H
Only sigma bonds shown
C C

H H

P-orbital overlap to form a

∏ bonds and ∏ electron H C
C H

clouds present above and

C C
below the plane of the ring.

H H
 Aromatic Character And Huckle’s Rule (4n+2):
 Aromatic compounds are highly unsaturated but resistant to
addition reaction.
 Low heat of hydrogenation
are low, so an usually
Low heat of combustion stable

 Electrophilic susbstitution

 They are cyclic compounds containing generally 5, 6 or 7

membered ring and are flat
 Aromatic

Delocalised ∏ electrons above and below the plane

Total of (4n+2) ∏ electrons (2,6 or 10)

This requirements are called as the 4n+2 rule or Huckle Rule.

 
 Eviences:

 Benzene 6∏ electrons (aromatic sextet) Huckle No n = 1.

 E.g: Naphthalene, anthracene and phenanthrene.

 2. Hetercyclic compounds – Pyridine, pyrrole, thiphene and

furan.
 +

..
+

 Aromaticity – a monocyclic compounds is aromatic if it

has a reasonably planar cyclic structure has (4n+2) ∏
electrons and possess unusual stability due to
delocalization of ∏ - electrons.
 Resonance structure of Benzene:

Or

 Resonance hybrid of the following structure.

Each single bond has some double bond character. All the
six C-C bonds are equivalent.

Hybrid
Nomenclature:
 Substituted benzenes. E.g: Chlorobenzene.

 Substituent along with benzene ring are given a new base

name.
E.g: Methylbenzene (C6H5CH3) – Toluene.

 When the substituent’s are present  relative position 

prefix ortho, meta, and para.
Br

Br

O-dibromo benzene
 If more than two substituted are present relative positions use
No
of numbers.
2

Br

2,4-Dibromo-1-nitrobenzene
Br

 A substituent “X” which when takes together with benzene ring

has a separate basis name C-atom bearing “X” is numbered.
NH2

Br Br
2,4,6-Tribromo aniline

Br

 C6H5 - R If R contains more C-atoms it is named as phenyl

substituted alkane.
H
CH3 C CH2 CH3

2-Phenylbutane C6H5
ELECTROPHILIC AROMATIC SUSBSTITUTION:
Benzene ring source of electronsacts as a base. so
electrophilic reagents can attack benzene.
 Nitration:
H2SO4
ArH + HONO2 ArNO2 + H 2O

Mechanism:
HONO2 + 2H2SO4 H3O+ + 2HSO4- + +NO2

Nitronium Ion
HH H
+
+
NO2 + C6H6 C6H5 Slow

H NO2
+
C6H5 + HSO4- C6H5NO2 + H2SO4 Fast

NO2

i) H2SO4 makes HNO3 OH- + NO2+

H
+
ii) Carbocation Formation C6H5 Benzonium Ion

NO2
 H NO2 H NO2 H H NO2
NO2
+ +
H H
+

H Resonance hybrid

I II III IV

 The base HSo4- abstracts the hydrogen ion to yield the

substitution product.

 Loss of hydrogen typical reaction of carbocation.

 Sulphonation:
i) 2H2SO4 H3O+ + HSO4- + SO3

Sulphonium Ion
O
Electrophile SO3 is generated S O
O
ii) Carbocation Formation H
+
SO3 + C6H6 C6H5 Slow

SO3

iii) Loss of Hydrogen ion to form susbstitution products

H
+
C6H5 + HSO4- C6H5SO3- + H2SO4 Fast
SO3
iv) C6H5SO3- + H3O+ C6H5SO3H + H2O

Equilibrium shift to the left

 Halogenation:
Fe
ArH + Cl2 ArCl + HCl
Aryl chloride
Fe
ArH + Br 2 ArBr + HBr
Aryl bromide
Mechanism:

_ +
Cl2 + FeCl3 Cl3 Fe Cl Cl (II)

_ +
+
Cl3 Fe Cl Cl C6H5 + FeCl4- Slow

Cl
+ H

C6H5 + FeCl4- C6H5Cl + HCl + FeCl3 Fast

Cl

Ferric chloride combine with Cl 2 to form complex – II from which it is transferred without
its electrons directly to the ring.
 Friedel crafts alkylation:
AlCl3
ArH + RCl ArR + HCl
Alkyl benzene
i) RCl + AlCl3 AlCl4- + R
Aryl bromide
H
+
ii) R + C6H6 C6H5 Slow

H R
+
iii) C6H5 + AlCl4- C6H5R + HCl + AlCl3 Fast

R
Cl

+
Cl Al Cl Cl R + C6H6

Cl
H
+
C6H5 + AlCl3 Slow

R
 Friedel crafts acylation:
AlCl 3
ArH + RO Cl A rCOR + H Cl
A cyl chloride K etone
+
- O
i) RC OC l + A lC l 3 A lC l 4 + RC
H
+ +
ii) A rH + RC O Ar

CO R
H
+
iii) Ar + A lC l 4 - Ar C R + A lC l 3

CO R
O
+
Attacking agent RC O

One of the important methods of preparing ketones.

 
 Protonation:
H2 O
ArSO3H + H + ArH + H2SO4 Desulfonation

ArH + D+ ArD + H+ Hydrogen exchange

+ H

C6H5SO3- + H+ C6 H 5

SO3-
+ H

C6H5 C6H6 + SO3

SO3-

 Electrophile is proton H+
 
 Reduction is Protonation (Protodesulphonation)
 Nitrosation:
ArH + HONO ArN O + H2O Only for Highly Reactive ArH
Nitroso compound

Attacking reagent is +NO/H2O+ and -NO or NOCl that can

easily transfer +NO to the ring.

 Diazo coupling:
G G G

+ ArN2+ +
+ H+

H N=NAr

Para directing N=NAr

 Klobe Reaction: Only for Phenol.
ONa OH OH

.
125 C
COONa COOH

+ CO2 4 - 7 atm H+

Sodium salicylate Salicylic acid

 Reimer-Tiemann Reaction:
OH O- O- OH

.
70 C
CHCl2 CHO CHO

CHCl3/ aq.NaOH HCl

O- O-
O
H
CHCl2

+ : CCl2
CCl2
-
Electrophilic Reagent
 Mechanism:

H
+ +
i) ArH + Y Ar Slow rate determinating step
Y

H
ii) Ar
+ + :Z ArY + H : Z Fast

 Attack by an electrophilic reagent upon the ring to form a carbocation.

 Abstraction of a hydrogen ion from carbocation by a base.

REACTIVITY & ORIENTATION:
H
+
C6H6 + Y+ C6H5

H Y H Y H Y H Y
H
H
+ +
+

+
Resonance hybrid
H

I II III IV
 Theory of Reactivity:
H Y H Y H Y

+ + +

NO 2
CH 3
Toluene
I II III

H δ+ Y
H Y

δ+ +

Stabilises carbocation Full +Ve Charge

 Inductive effect  stabilises transition state.

 No2 groupelectron withdrawing inductive effect 

intensifies positive charge  destabilises carbocation. So
slower reaction.

 A group that release electrons  activates NH2, OH, OCH3,

NHCOCH3 and C6H5CH3.

 A group that withdraws electrons  deactivates –N(CH3)3+,

-NO2, -CN, -SO3H, COOH, CHO & COR.
THEORY OF ORIENTATION:
 The effect of any group whether activating or deactivating is
the strongest at the ortho and para positions.

CH 3 CH 3 CH 3

PAR A ATTACK

H Y H Y H Y

Spacially Stable
CH 3 CH 3 CH 3

H H H
M ETA ATTACK

Y Y Y
No Positive charge on carbon attached to CH 3
 Deactivating group:
NO2 NO2 NO2

PARA ATTACK

H Y H Y H Y
M o s t u n s ta b le
NO2 NO2 NO2

H H H M ETA ATTACK

Y Y Y

NO2 NO2 NO2

H H H

ORTHO ATTACK
Y Y Y

H ig h l y u n s t a b l e

In nitrobenzene, ortho, para substitution is thus slower than the

meta substitution.