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ElectropHilic
Aromatic
Sustitution
 QUIZRR 3

ElectropHilic Aromatic Sustitution

1. AROM ATI CI TY

H H
C C
HC CH HC CH

HC CH HC CH
C C
H H

In organic chemistry, the structures of some rings of atoms are unexpectedly stable. Aromaticity
is a chemical property in which a conjugated ring of unsaturated bonds, lone pairs, or empty
orbitals exhibit a stabilization stronger than would be expected by the stabilization of conjugation
alone. It can also be considered a manifestation of cyclic delocalization and of resonance.
This is usually considered to be because electrons are free to cycle around circular arrangements
of atoms, which are alternately single and double-bonded to one another. These bonds may be seen
as a hybrid of a single bond and a double bond, each bond in the ring identical to every other. The
benzene consists of two resonance forms, which corresponds to the double and single bondsÊ switching
positions. Benzene is a more stable molecule than would be expected without accounting for charge
delocalization.

1 .1 T h e o r y
H
H H

H H
H

A C=C bond is shorter than a CăC bond, but benzene is perfectly hexagonalăall six carbon-carbon
bonds have the same length, intermediate between that of a single and that of a double bond.
A better representation is that of the circular  bond in which the electron density is evenly
distributed through a -bond above and below the ring. This model more correctly represents the
location of electron density within the aromatic ring.

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The single bonds are formed with electrons in line between the carbon nucleiăthese are called
-bonds. Double bonds consists of a -bond and a -bond. The -bonds are formed from overlap of
atomic p-orbitals above and below the plane of the ring. The following diagram shows the positions
of these p-orbitals :

Side view Projection

Since they are out of the plane of the atoms, these orbitals can interact with each other freely,
and become delocalised. This means that instead of being tied to one atom of carbon, each electron is
shared by all six in the ring. Thus, there are not enough electrons to form double bonds on all the
carbon atoms, but the „extra‰ electrons strengthen all of the bonds on the ring equally. The resulting
molecular orbital has  symmetry.

H H

H H H H
H H
H H

6-p-orbitals delocalised orbital clouds

1 .2 Ch a r a c t e r i s t i c s o f a r o m a t i c (A r yl ) c o m p o u n d s
An aromatic compound contains a set of covalently-bound atoms with specific characteristics :
1. A delocalized conjugated  system, most commonly an arrangement of alternating single
and double bonds.
2. Coplanar structure, with all the contributing atom in the same plane.
3. Cyclic in nature
4. A number of  delocalized electrons that is even, but not a multiple of 4. That is, 4n +
2 of  electrons, where n = 0, 1, 2, 3 and so on. This is known as HuckelÊs Rule.
l Aromatic molecules typically display enhanced chemical stability, compared to similar non-
aromatic molecules. A molecule that can be aromatic will tend to alter its electronic or
conformational structure to be in this situation. This extra stability changes the chemistry
of the molecule.
l Many of the earliest-known examples of aromatic compounds, such as benzene and toluene,
have distinctive pleasant smells. This property led to the term „aromatic‰ for this class of
compounds, and hence the term „aromaticity‰ for the eventually-discovered electronic property.

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1 .3 A n t i a r o m a t i c i t y
+ ·
C C

A B C Cyclooctatetraene

Antiaromatic molecules are cyclic systems containing alternating single and double bonds,
where the pi electron energy of antiaromatic compounds is higher than that of its open-chain
counterpart. Therefor antiaromatic compounds are unstable and highly reactive; often antiaromatic
compounds distort themselves out of planarity to resolve this instability. Antiaromatic compounds usually
fail HuckelÊs rule of aromaticity.
Examples of antiaromatic systems are cyclobutadiene (A), the cyclopentadienyl cation (B) and
the cyclopropenyl anion (C). Cyclooctatetraene is a 4n system but neither aromatic or antiaromatic
because the molecule escapes a planar geometry.
By adding or removing an electron pair via a redox reaction, a  system can become aromatic
and therefore more stable than the original non- or anti-aromatic compound, for instance the
cyclooctatetraenide dianion. The IUPAC criteria for antiaromaticity are as follows :
1. The molecule must have 4n  electrons where n is any integer.
2. The molecule must be cyclic.
3. The molecule must have a conjugated pi electron system.
4. The molecule must be planar.

Ex a m p l e 1
Is this compound aromatic or antiaromatic ?

N
Solution :
The given compound, pyridine is aromatic as total no. of conjugated electrons
= 6 = 4n + 2 where n = 1.
Here lone pair of Nitrogen is not involved in delocalisation.

EX CEPT I ON S
(1 )

H H

Here no. of  eă = 10

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Molecule will be aromatic if planar. But due to the repulsion between hydrogens, molecule lose
its planarity.
(2 )

Here no. of  eă = 8
This molecules should be antiaromatic.
But its not planar. Its real structure is non planar.

Nonplanar

Therefore this molecule is nonaromatic.

1 .4 St a b i li t y o f Co m p o u n d s
Order of stability is :
aromatic > nonaromatic > antiaromatic
Stability order is explained on basis of constructive and destructive resonance in aromatic and
antiaromatic compound respectively; which comes under molecular orbital theory.

1 .5 Cy c l o p r o p e n i u m s a l t s
H
+

H H
This is the cyclopropenyl cation and may be represented as a resonance hybrid.

H H H H
+ +

+ +
H H H H H H H H

Hence the cyclopropenyl cation should be stable. Many cyclopropenium salts have actually been
prepared.

ELECTROPHILIC AROMATIC SUBSTITUTION

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e.g. (i) hydroxydiphenyl propenyl bromide

(ii) cyclopropenyl hexachloroantimonate.

Ph Ph
O H·Br OH Br·
(i)
Ph Ph

·
(ii) Cl SbCl5 SbCl6

1 .6 Cy c l o b u t e n i u m s a l t s

Br
Ph Ph
Ph1 Ph
2AgBF4
++ 2BF4
Ph Ph
Ph Ph
Br

1 .7 A n n u l e n e s
Conjugated monocyclic polyenes, CnH n, in which n  10 are usually called onnulenes.
The annulenes prepared have n = 12, 14, 16, 18, 20, 24 and 30, of these only [14], [18] and [30]
annulenes are (4n + 2) electron molecules and rest ore 4n molecules.

H
H H
H H
HH H HHH
H

dehydro
[14] annulene [18] annulene [14] annulene

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1 .8 A zu l e n e

Azulene

+ ă

dipolar structure

There are two KeKule resonating structures containing 10  electrons (n = 2; and 10 peripheral
-electrons). The five membered ring has five and the seven membered ring has seven electrons (two
electrons are common to both rings). If one electron is transferred from seven to the five ring each
ring will now have a closed shell of six electrons. In this condition, the molecule will have a dipolar
structure.

2. EL ECT ROPH I LI C A ROM A T IC SU B ST I T U T ION

Overall an electrophilic aromatic susbtituton can be represented as follows :

E
E+ + + H+

There are three fundamental compounds to an electrophilic substitution reaction :

1. Formation of the new  bond from a C=C in the arene nucleophile
2. removal of the proton by breaking the C-H  bond
3. reform the C=C and restore aromaticity

E
H E
E+
+ H+
+

The mechanism is represented by the following series of events :

l Formation of the reactive electrophile, E+
l Slow reaction of the arene C=C with the E+ to give a resonance stabilised carbocation (see
below)

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l Loss of H+ from the carbocation to restore the C=C and the aromatic system

+
E E E

+ +

The reaction of the electrophile E+ with the arene is the slow step since it results in the loss of
aromaticity even though the resulting cation is still resonance stablised.

Wh y Su b s t i t u t i o n n o t A d d i t io n ?
Overall an electrophilic aromatic substitution can be represented as follows :

E
E+ + + H+

But we have previously seen the C=C generally react via an electrophilic addition pathway :

E
Nu·E + =
Nu

So why donÊt arenes react in a similar fashion to alkenes and give overall addition ?
The first step is common to both, E
E + adds a C=C to give a
E+
carbocation intermediate. +

For an addition pathway, the

E E
nucleophile then adds to the
electrophilic carbocation giving Nuă
+ addition
a cyclohexadien e derivative. Nu

For a substitution pathway

„nucleophile‰ functions as a base E
H E
and removes a proton from the
sp3 C to recreate the C=C and Nuă + NuH
+ substitution
restore the aromaticity.
The resonance energy of benzene is about 152 kJ / mol (36 kcal / mol) and a conjugated diene
is 16 kJ / mol (4 kcal / mol).This extra stability of the aromatic system is responsible for favouring the
substitution reaction.

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l An electrophilic substitution reaction on benzene does not always result in monosubstitution.

While electrophilic substituents usually withdraw electrons from the aromatic ring and thus
deactivate it against further reaction, a sufficiently strong electrophile can perform a second
or even a third substitution. This is especially the case with the use of catalysts.

3 . SOM E B A SI C REA CT I ON S
3 .1 N i t r a t i o n

Arom at ic nit rat ion

In a aromatic nitration, aromatic organic compounds are nitrated via an electrophilic
aromatic substitution mechanism involving the attack of the electron-rich benzene ring by the
nitronium ion.

H2SO4
+ HNO3 NO2 + H2O

Benzene is nitrated by refluxing with concentrated sulfuric acid and concentrated nitric acid at
50ĈC. The sulfuric acid is regenerated and hence acts as a catalyst. It also absorbs water.
The formation of a nitronium ion (the electrophile) from nitric acid and sulfuric acid and subsequent
reaction of the ion with benzene is shown below :

NO2 H2SO4 + NO2 H2SO4 + ă

H·O H·O NO2 + H3O + HSO4

H
+
HSO4


   
i.e. HNO3  2H2SO4  NO2  H3O  2HSO4

Now the NO2+ ion attacks the benzene nucleus and forms an intermediate cation, a benzenonium
ion; which loses a proton to yield the nitro derivative.

H
electrophilic
+ NO2 NO2 NO2
attack
Nitronium
ion

NO2 H H
+ NO2 NO2
H +

Nitro benzene

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The nitronium ion is well known existing in salts such as NO2 ClO4 and NO2 BF4 which
smoothly nitrate benzene at room temperature. It supports the mechanism in which the electrophile
species attacking the aromatic compound is nitronium ion NO2 .
Highly reactive aromatic compounds such as phenol, are found to undergo ready nitration even
in dilute nitric acid and at a far more rapid pace than can be explained on the basis of the
concentration of NO
2 that is present in the mixture. This has been shown due to the presence of 
nitrous acid in the system which nitrosates the reactive nucleus via the nitrosonium ion N O .



  
HNO2  2HNO3 
 H3O  2NO3  NO

OH OH OH OH

NO NO3 HNO3 + HNO2

H NO NO NO2

3 .2 .1 So m e I m p o r t a n t Po i n t s

NO2 can be generated by :

(i) Mixture of HNO3 & any other acid stronger than HNO3 to generated NO2 .

HNO3 / conc. H2SO4

It is behaves base It is behaves as an acid

H2 SO4  OH  NO 2  NO 2  HSO4  H2O

(ii) Conc. HNO3 + HO-NO2  NO2 + H2O + HNO3ă

(iii) N2O5  NO2 + NO3ă

 
(iv) NO2 BF4ă  NO2 + BF4ă

Ist step is slow step mechanism because compound loses its aromaticity.
In IInd step compound gains aromaticity, it is highly fast.
Potential energy curve with the progression of reaction is given by :

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Slowstep (step1)

Fast step (step2)

P.E.

reaction coordinate
progression of reacter

If H in Benzene is replaced by D, then

D D
D D D E+
+ D
+E
D D D D
D D

ăD+

Here E+ = NO2

Co m p a r is o n o f r a t e s
Let for the first reaction the value of rate constant is kH and that for IInd is kD then which can
be true.
(i) kH > kD
(ii) kH < kD
(iii) kH = kD
(iv) canÊt say Ans. : KH > KD

Ex p l a n a t i o n
C ă D bond is stronger than C-H.

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3 .2 A r o m a t i c Su l f o n a t i o n
Aromatic sulfonation is an organic reaction in which a hydrogen atom on an arene is
replaced by a sulfonic acid functional group in an electrophilic aromatic substitution.

Heat
+ H2SO4 SO3H + H2O

Sulfur trioxide is the electrophile in this reaction generated from concentrated sulfuric acid
(or fuming sulfuric acid) when heated.
O O O O

HO S OH + HO S OH HO S OH2+ + ăO S OH

O O O O

HO S + H2O SO3 + H3O+

O
ă
ă 
O O O O O

S S+ S+ S+ S ă
ă ă ă 
O O O O O O O O  O O
l In contrast to aromatic nitration and other electrophilic aromatic substitution this reaction
is reversible. Sulfonation takes place in concentrated acidic conditions and desulfonation is
the mode of action in a dilute hot aqueous acid.

Mec hanism of sulphonat ion

ă H
O
SO3
+
+ S
O O

H
SO3H H SO3
SO3

S is bonded to three more electronegative oxygen atoms. Hence, S is electron deficient, acting as
electrophile.

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M o r e I m p o r t a n t Po i n t s
Increase of sulphonation the electrophile is SO3.
l SO3 has vacant orbital, therefore it is electrophile.
l Both the steps are in equilibrium in the mechanism.

Co m p a r is o n w it h De u t ro b e n ze n e :

D SO3D
D D D
D + H2SO4
D D D D
D D

KH > KD
This reaction is reversible.

En e r g y Pro f i l e

P.E.

Reaction coordinate

Reaction is reversible. Carbocation can proceed in both forward and backward direction. IInd step
is not the fast step. Both the step will contribute to stability of product.
C ă D bond is stronger than C-H bond.

3 .3 El e c t ro p h i li c h a l o g e n a t i o n
In organic chemistry, an electrophilic aromatic halogenation is also a type of electrophilic
aromatic substitution. This organic reaction is typical of aromatic compounds and a very useful
method for adding substituents to an aromatic system.

(catalyst)
+ X X + HX

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A few types of aromatic compounds, such as phenol, will react without a catalyst, but for typical
benzene derivatives with less reactive substrates, a Lewis acid catalyst is required. Typical Lewis
acid catalysts include AlCl3, FeBr3, and ZnCl2. These work by forming a highly electrophilic complex
which attacks the benzene ring.

Re a c t i o n m e c h a n i s m
+ ă ă
Br · Br + FeBr3 Br · Br ...... Fe Br3 Br+ + FeBr4
(catalyst)
ă
B
H
+ Br + Br + HB
Br

l The reaction mechanism for chlorination of benzene is the same as bromination of benzene.
Ferric bromide and ferric chloride become inactivated if they react with water, including
moisture in the air. Therefore, they are generated in situ by adding iron filings to bromine
or chlorine.
l Halogenation of aromatic compounds differs from the halogenation of alkenes, which do not
require a Lewis Acid catalyst. The formation of the arenium ion results in the temporary
loss of aromaticity, which has a higher activation energy compared to carbocation
formation in alkenes. In other words, alkenes are more reactive and do not need to have the
Br-Br or Cl-Cl bond weakened.

Im po rt an t po int
A similar dual mechanism can also operate when halogenation is carried out with hypochlorous
and hypobromous acid. The reaction is acid catalysed.
HăOăCl+H+  H2O+ăCl
H
Cl
+ H2O Cl +
+ H2O ă Cl +H
+

Ex a m p l e 4
Among pyrrole and pyridine, Which is more basic and why?

and
N
N
·

H
(pyrrole) (pyridine)

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Solution :
Pyridine is more basic than pyrrole because in case of pyridine nitrogen lone pair does not
participate in aromaticity.

Ex a m p l e 5
Write the product of mono bromination of C6H5CF3.
Solution :
F F
F F F F

FeBr2 + HBr
+ Br2
Br
ăCF3 shows (ă I) effect. Hence it is behave as M-directing group.

Ex a m p l e 6
Find out products in following conversion.
(i) C6H5CH (CH3)CH2CH2 (monosulfonation)  (A)

(ii)
(mononitration) (B)

Solution : H3 C
CH3

A

SO3 H
O O
CH3

B

NO2

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3 .4 Fr i e d e l -Cra f t s a l k y l a t i o n
Friedel-Crafts alkylation involves the alkylation of an aromatic ring and an alkyl halide
using a strong Lewis acid catalyst. With anhydrous Aluminium chloride as a catalyst, the alkyl
group attaches at the former site of the chloride ion. The general mechanism is shown below.

R  Cl  AlCl3  R   AlCl 4

Cl

·
ă
Cl · Al · Cl

·
+ H R
R R Cl

ă HCl
+ AlCl3 + HCl
+ catalyst regenerated
 ăcomplex
Im po rt an t po int s
1. This reaction has one big disadvantage, namely that the product is more nucleophilic than
the reactant due to the election donating alkyl-chain. Therefore, another hydrogen is
substituted with an alkyl-chain, which leads to overalkylation of the molecule.
2. Also, if the chlorine is not on a tertiary carbon, carbocation rearrangement reaction
will occur. This is due to the relative stability of the tertiary carbocation over the secondary
and primary carbocations.
Alkylations are not limited to alkyl halides : Friedel-Crafts reactions are possible with any
carbocationic intermediate such as those derived from alkenes.
3. Not only nature of alkyl group, but also temperature determines the nature of electrophile.
e.g. n-alkyl group can be introduced to a fair extent without rearrangement at low
temperature, because ionisation of oduct is retarted. But at higher temperature, carbonium
ion is formed which rearranges and the product is rearranged alkyl benzene. Thus n-
propylchloride gives isopropyl benzene.

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CH3
CH2 · CH2 · CH3 + AlCl3 + HCl
CH
CH3
+ AlCl3 + HCl

4. The order of effectiveness of Lewis acid catalysts has been shown to be

AlCl3 > FeCl3 > BF3 > TiCl3 > ZnCl2 > SnCl4
The action of Me3CCH2/AlCl3 on benzene is found to yield almost completely the rearranged
product PhCMe2 CH2Me, while Me3CCH2Cl/FeCl3 on benzene is found to yield almost
completely the unrearranged product.

3 .4 .2 Fr i e d e l -Cra f t s a c y l a t i o n
l Friedel-Crafts acylation is the acylation of aromatic rings with an acyl chloride using a
strong Lewis acid catalyst.
l Friedel-Crafts acylation is also possible with acid anhydrides.
l Reaction conditions are similar to the Friedel-Crafts alkylation mentioned above. This reaction
has several advantages over the alkylation reaction. Due to the electron-withdrawing effect
of the carbonyl group, the ketone product is always less reactive than the original molecule,
so multiple acylations do not occur. Also, there are no carbocation rearrangements, as the
carbonium ion is stabilized by a resonance structure in which the positive charge is on the
oxygen.
O

RCOCl or (RCO)2O
R
AlCl3 catalyst reflux
anhydrous conditions

Re a c t i o n m e c h a n i s m
In a simple mechanism view, the first step consists of dissociation of a chlorine atom to form an
acyl cation

O
+ ă
R ă C ă Cl + AlCl3 R ă C = O + AlCl4

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This is followed by electrophilic acylcation toward the arene.

+
+RăC=O

Finally, a chlorine atom reacts to form HCl, and the AlCl3 catalyst is regnerated.
O
O
H CăR
C
ă
+ AlCl4 R
+ HCl + AlCl3

Product

L i m i t a t io n s o f Fr ie d e l -Cr a f t s r e a c t i o n s
Several restrictions limit the usefulness of Friedel-Crafts reactions :
(1) When the carbocation formed from an alkyl halide, alkene, or alcohol can rearrange to a
more stable carbocation, it usually does so and the major product obtained from the reaction
is usually the one from the more stable carbocation. When benzene is alkylated with butyl
bromide, for example, some of the developing butyl cations rearrange by a hydride shift ă
some developing 1Ĉ carbocations (see following reactions) become more stable 2Ĉ carbocations.
Then benzene reacts with both kinds of carbocations to form both butylbenzene and sec-
butyl benzene.
+
CH2 CH3
AlCl3
Br +
H3 C H3 C H3 C

CH3
H3C

butylbenzene sec-butylbenzene

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(2) Friedel-Crafts reactions do not occur when powerful electron-withdrawing groups are present
on the aromatic ring or when the ring bears an ăNH2, ă NHR, or ăNR2 group. This applies
to alkylations and acylations.
O OH O R
+ +
NO2 N(CH3 )3 C C CF3 SO3H NH3

These do not undergo Friedel-Crefts reactions

We shall learn that the groups present on an aromatic ring can have large effect on the
reactivity of the ring towards electrophilic aromatic substitution. Electron-withdrawing groups
make the ring less reactive by making it electron deficient. Any substituent more electron
withdrawing (or deactivating) than a halogen, that is, any meta-directing group, makes an
aromatic ring too electron deficient to undergo a Friedel-Crafts reaction. The amino groups,
ăNH2, ă NHR, and ăNR2 are changed into powerful electron-withdrawing groups by the
Lewis acids used to catalyze Friedel-Crafts reactions. For example :
H
H H
·

+
·

N H · N · AlCl3

+ AlCl 3

Does not undergo a

Friedel-Crafts reaction

(3) Aryl and vinyl halides cannot be used as the halide component because they do not form
carbocations readily. Cl

No Friedel-Crafts reaction
AlCl3

No Friedel-Crafts reaction
CH3

Cl
H3 C

CH3

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(4) Polyalkylations often occur. Alkyl groups are electron -releasing groups, and once one is
introduced into the benzene ring it activates the ring toward further substitution.

H3C CH3 H3C CH3

H3C
BF3
+ OH +
60Ĉ C
H3C Isopropyl benzene (24%)

H3C CH3
p-disopropylbenzene (14%)

Polyalkylations are not a problem in Friedel-Crafts acylations, however the acyl group
(RCOă) by itself is an electron-withdrawing group, and when it forms a complex with AlCl3
in the last step of the reaction, it is made even more electron withdrawing. This strongly
inhibits further substitution and makes monoacylation easy.

Ex a m p l e 7
What happens when benzene is treated with methyl chloride in presence of anhydrous
AlCl3 and the product is treated with excess of chlorine in presence of UV light ?
Solution :

anhy Cl2 Cl2 Cl2  C H CCl

C6 H6  CH3Cl  C6 H5CH3   C6 H5CH2Cl   C6 H5 CHCl2  6 5 3
Benzene
AlCl3 UV light Benzotrichloride

Co m p a r is o n b e t w e e n a l k y l a t i o n a n d a c y l a t i o n
(i) A comparison of the electrophilic nature of both alkyl and acyl group indicates that acyl
group is a better electrophile on account of two electron withdrawing atoms attached to C.

H
ă
·

+ ă O
R · C · Cl
·
·
·

R · C · Cl
H +

Effective +ve charge density

on carbonyl compound is greater.

(ii) Acylation requires more catalyst than alkylation because much of the catalyst is removed by
the formation of a complex with the product (ketone) and is removed from further participation
in the reaction.

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ă
H3C · C O AlCl3
COCH3 +
+ AlCl3

(iii) Unlike polyalkylation, polyacylation does not take place as the product ketone is much less
reactive than the original hydrocarbon.
(iv) Rearrangement of R does not take place in acylation, but decarbonylation can take place,
especially where R would form a stable carbonium ion, so that the end result is then
alkylation rather that the expected anylation.


e.g. Me3 C  C  O  CO  Me3 C

CHe3
+
+ Me3 C

3 .5 So m e I m p o r t a n t Re a c t io n s

(1) Reaction of alcohols + Acid +

Solution :

(i) CH3 CH2OH + H+ ?

CH2CH3

H
+ +
CH3CH2 · O CH3CH2
H

(ii) CH2 OH

+
+H

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+
CH2OH CH2

+
Solution : + Rearrangement
H

(2) Reaction of Alkene + Acid +

CH3
| +
(i) H
CH3  CH  CH  CH2

Solution :

CH3 CH3
| |
H
CH3  CH  CH  CH2   CH3  CH ă CH  CH3
+

1, 2 hydride shift

CH3 CH3
·

CH3 · C · CH2 CH3 CH3 · C · CH2CH3

+
·

ELECTROPHILIC AROMATIC SUBSTITUTION

 24 QUIZRR

(3) Reaction of Alkyl Halide + Lewis Acid +

CH3
·
AlCl
3
(i) CH3 · C · CH2Cl
·

CH3

CH3 CH3
| |
CH3  C  CH 2Cl
AlCl3
  CH3  C  CH ă
2  AlCl 4
| |
CH3 CH3

Rearrangement

CH3 CH3
·

·
CH3 · C · CH2 CH3 CH3 · C · CH2 · CH3
+
·

Ex a m p l e 8

AlCl3
+ O

+
Solution : ă
+ AlCl3 OAlCl3
O

OH O ă AlCl3
H
+
AlCl3 +

ELECTROPHILIC AROMATIC SUBSTITUTION

 QUIZRR 25

O
(3)
AlCl3
+ O O

O OH
O O
O
+
O + AlCl3 ă
O AlCl3

O O
H3 C O
O C
·
·

(4) + CH3 · C · AlCl3

O
·
H3 C · C
·
·

O
Table for reactions
Reaction Reagents Electrophile Product Comments
NO2

Nitration HNO3 / H2SO4 NO2 E+ formed by loss of water

from nitric acid

SO3H

Sulfonation H2SO4 or SO3/H2SO4 SO3 Reversible

Cl

Halogenation Cl2/Fe or FeCl3 Cl+ E+ formed by Lewis acid

removing Clă

Br

Br2/Fe or FeBr3 Br+ E+ formed by Lewis acid

removing Bră
R

Alkylation R-Cl/AlCl3 R+ E+ formed by Lewis acid

removing Clă

ELECTROPHILIC AROMATIC SUBSTITUTION

 26 QUIZRR

R-OH/H+ R+ E+ formed by loss of water

from alcohol

C=C/H+ R+ E+ formed by protonation

of alkene
O

CR
Acylation RCOCl/AlCl3 RCO+ E+ formed by Lewis acid

removing Clă
O

CR
RCO2COR/AlCl3 RCO+ E+ formed by Lewis acid

removing RCO2

Ex a m p l e 9
Deduce the structure of compound A, C9H8 from the following experimental data :
A decolorizes Br2 in CCl4 and adds one eq. of H2 under mild conditions, forming B, C9H10.
At high temperature and pressure A adds four eq. of H2.Vigorous oxidation of A yields
phthalic acid, 1, 2ăC6H4(COOH)2.
Solution :
A has 6Ĉ of unsaturation, four of which often signal the presence of benzene ring, as confirmed
by isolation of phthalic acid on vigorous oxidation. Reaction with Br2 and one eq. of H2 indicate there
is a C=C. Addition of three more eq. of H2 further indicates the presence of a benzene ring. So far 5Ĉ
of unsaturation have been accounted for ăthe sixth degree resists reduction and must be a ring with
C=C. Oxidation to the ortho-dicarboxylic acid indicates the ring is fused to the benzene ring. The
structure is indene.

COOH
(O) H2 3H2

COOH
Phthalic acid Indene, (A) Indane, (B) Bicyclo (4.3.0) nonane

ELECTROPHILIC AROMATIC SUBSTITUTION

 QUIZRR 27

Ex a m p l e 1 0
(a) Give the structures for all possible chiral compounds, C10H12, that do not decolorize
Br2 and that can be oxidized to phthalic acid.
(b) Identify E, also chiral, with the same formula, but which is oxidized to PhCOOH.
Solution :
(a) The formula reveals a fifth degree of unsaturation in addition to the four of the benzene
ring. This fifth degree of unsaturation must be a ring, not C=C, because the Br2 test is
negative. Production of phthalic acid means the ring is fused to the benzene ring. This fused
ring has the chiral carbon and must be a monoăRăsubstituted fiveămembered or diăRă
substituted fourămembered ring. Only in this way can we account for the additional four
CÊs of the formula.
H Me H
Me
H Et
H
Me
1-Methylindane trans-1,2-Dimethylbenzcyclobutane 1-Ethylbenzcyclobutane

(b) The extra unsaturation is in the single side chain. E is 3ăphenylă1-butene,

CH3  CHCH  CH2

|
Ph

3 .6 Su b s t i t u t e d a r o m a t i c r in g s
1. Electrophiles may attack aromatic rings with functional groups. Performing an electrophilic
substitution on an already substituted benzene compound raises the problem of addition. In
case of a monosubstituted benzene, there are 4 different reactive positions. For a
monosubstituted benzene, the ring carbon atom bearing the substituent is position 1 or
ipso, the next ring atom is position 2 or ortho, position 3 is meta and position 4 is para.
Positions 5 and 6 are respectively equal to 3 and 2.
2. Substituents can generally be divided into two classes regarding electrophilic substitution :
activating and deactivating towards the aromatic ring. Activating substituents or
activating groups stablize the cationic intermediate formed during the substitution by
donating electrons into the ring system, by either inductive effect or resonance effects.
Examples of activated aromatic rings are toluene, aniline and phenol.
3. The extra electron density delivered into the ring by the substituent is not equally divided
over the entire ring, but is concentrated on atoms 2, 4 and 6 (the ortho and para positions).
These positions are thus the most reactive towards an electron-poor electrophile. The highest
electron density is located on both ortho positions, though this increased reactivity might be

ELECTROPHILIC AROMATIC SUBSTITUTION

 28 QUIZRR

offset by steric hindrance between substituent and electrophile. The final result of
the electrophile aromatic substitution might thus be hard to predict, and it is usually
only established by doing the reaction and determining the ratio of ortho versus para
substitution.
4. On the other hand, deactivating substituents destablize the intermediate cation and
thus decrease the reaction rate. They do so by withdrawing electron density from the
aromatic ring, though the positions most affected are again the ortho and para ones. This
means that the most reactive positions (or, least unreactive) are the meta ones (atoms 3
and 5). Examples of deactivated aromatic rings are nitrobenzene, benzaldehyde and
trifluoromethylbenzene.
5. Functional groups thus usually tend to favour one or two of these positions above the others;
that is, they direct the electrophile to specific positions. A functional group that tends to
direct attacking electrophiles to the meta positions, for example is said to be meta-directing.

3 .6 .1 Or t h o /p a r a d i r e c t o r s
Groups with unshared pairs of electrons, such as the amino group of aniline, are strongly
activating and ortho/ para-directing. Such activating groups donate those unshared electrons to the
pi system.
NH2

+
A

H + H
NH2 NH2 N NH2
H + H H H
C
A A A A
+ +
C C
H H
+
ăH

NH2

ELECTROPHILIC AROMATIC SUBSTITUTION

 QUIZRR 29

When the electrophile attacks the ortho and para positions of aniline, the nitrogen atom can donate
electron density to the pi system (forming an iminium ion), giving four resonance structures (as
opposed to three in the basic reaction). This substantially enhances the stability of the cationic intermediate.
NH2

+
A

+
ăH
H + H
NH2 NH2 N NH2
+
C
+
C C+
H H
A H A H A H A H

NH2

A
Compare this with the case when NH2

the electrophile attacks the meta position.

In that case, the nitrogen atom cannot
donate electron density to the pi system,
A
giving only three resonance contributors.
For this reason, the meta-substituted +
ăH H
product is produced in much smaller +
NH2 NH2 C NH2
proportion to the ortho and para products.
+
Other substituents, such as the C C+
alkyl and aryl substituents, may also H H
donate electron density to the pi system; A H A H A H
however, since they lack an available
unshared pair of electrons, their ability NH2
to do this is rather limited. Thus they only +
A
weakly activate the ring and do not
strongly disfavor the meta position.

ELECTROPHILIC AROMATIC SUBSTITUTION

 30 QUIZRR

3 .6 .2 Sp e c i a l Ef f e c t o f H a l o g e n s
l Halogens are ortho/ para directors, since they possess an unshared pair of electrons just as
nitrogen does. However, the stability this provides is offset by the fact that halogens are
substantially more electronegative than carbon, and thus draw electron density away
from the pi system. This destablizes the cationic intermediate, and EAS occurs less readily.
Halogens are therefore deactivating groups.
Hence we can say that halogens are de-activating yet ortho, para directing.
A halogen substituted benzene (C6H5-X) by virtue of the presence of unshared electron pair on
the halogen, exhibits resonance. Thus it can be represented by the resonance hybrid of following :
+ +
X X X

+ +
X X X

ă ă ă

ă
Halogens withdraw electrons through its inductive effect (ă I) and releases electrons through its
resonance or mesomeric effect (+ M). Thus for halogen, the two effects are more evenly balanced and
we observe the operation of both.

3 .6 .3 M e t a d i r e c t o r s
Non-halogen groups with atoms that are more electronegative than carbon, such as the nitro
group (NO2) draw substantial electron density from the pi system. These groups are strongly
deactivating groups. Additionally, since the substituted carbon is already electron-poor, the resonance
contributor with a positive charge on this carbon (produced by ortho/ para attack) is less stable than
the others. Therefore, these electron-withdrawing groups are meta directors. ăCF3, ăCCl3, ăCBr3, ăCl3
are meta directors.
Electron withdrawing groups (EWG) with  bonds to electronegative atoms (e.g. ăC=O, ă
NO2) adjacent to the  system deactivate the aromatic ring by decreasing the electron density on the
ring through a resonance withdrawing effect. The resonance only decreases the electron density at
the ortho- and para- positions. Hence these sites are less nucleophilic, and so the system tends to react
with electrophiles at the meta sites.

ELECTROPHILIC AROMATIC SUBSTITUTION

 QUIZRR 31


W ăW ăW ăW W

+ + +

+ +

l The deactivation of the aromatic system also means that generally harsher conditions are
required to drive the reaction to completion. An example of this is the nitration of toluene
during the production of trinitrotoluene (TNT). While the first nitration, on the activated
toluene ring, can be done at room temperature and with dilute acid, the second one, on the
deactivated nitrotoluene ring, already needs prolonged heating and more concentrated acid,
and the third one, on very strongly deactivated dinitrotoluene, has to be done in boiling
concentrated sulfuric acid.

Ex a m p l e s :
When the substituent has at least one strongly electronegative atom and a multiple bond
in conjugation with benzene ring :
Let ăA = B represent the group in which B is more electronegative than A. The highly electronegative
atom pulls the electron pair of the multiple bond which is form withdraws electron from benzene ring
(ăM effect) giving rise to the following five cononical forms :

ă ă
A= B A· B A· B

+
I II

ă ă
A B A= B Aă B

+ + +

+

Evidently electrons are withdrawn by the substituent group from the ring and more so from
ăO ăP positions where electron density declines. Also, the meta positions have relatively more electron
density and therefore electrophilic substitution takes place at the meta positions.

ELECTROPHILIC AROMATIC SUBSTITUTION

 32 QUIZRR

The nitro and sulphuric acid groups are examples of the type of electron withdrawing substituents
which one characterized by the presence of a strong electronegative atom attached to another more
electronegative atom by a multiple bond.

Ex a m p l e 1 1
Draw the resonance structure for electrophilic substitution reactions of nitro benzene and
explain why it is meta-directing group ?
Solution : NO2 NO2 NO2
H H H
+ +
E E E E
NO2
ortho
+ +
(A)
NO2 NO2 NO2

+
Para
+ +
(B)
H E H E H E

NO2 NO2 NO2

+ +

Meta H H H
(B) +
E E E
In ortho-para attack of electrophile on nitrobenzene, we are getting two structures (A) and (B)
in which positive charge is appearing on the carbon atom directly attached to the nitro group. As nitro
group is electron withdrawing by nature, it decreases the stability of such product and hence meta
attack is more feasible when electron withdrawing substituents are attached.

Ex a m p l e 1 2
Convert benzene  p-bromonitrobenzene
Solution :

Br Br Br

NO2
Br2 conc. HNO3
+ (Separate)
Fe conc. H2 SO4

NO2

ELECTROPHILIC AROMATIC SUBSTITUTION

 QUIZRR 33

Here is a table that shows the effect of substituents on a benzene ring have on both the rate and
orientation of electrophilic aromatic substitution reactions.
These effects are a combination of Resonance and Inductive effects. The effects are also
important in other reactions and properties (e.g. acidity of the substituted benzoic acids).

Here are some general pointers

·O
for recognising the substituent
· NR2 effects :
· NH2 Strongly Activating
· OH
l The H atom is the standard
· OR
and is regarded as having no
O
Activating effect.
·
·

· NHCR ortho
O Moderately Activating direct
·
·

EDG l Activating groups increase

· OCR
the rate
·R

l Deactivating groups
Weakly Activating
decrease the rate
· C = CR 2
H

Reference ·H
l EDG = electron donating
·X Weakly Activating group
O
·
·

· CH l EDG can be recognised by

O lone pairs on the atom
·
·

adjacent to the  system, eg :

· CR
OMe
·S·R
·
·

O Moderately deactivating
exc e p t -R, -Ar or -vinyl
·C·
l
·
·N
EWG Meta directed (hyperconjugation, electrons)
· C · OR
·
·

O
l EWG = electron
· C · Cl
·
·

withdrawing
O
·N·O
·

O
Strongly deactivating
· CF3
+
· NR3

ELECTROPHILIC AROMATIC SUBSTITUTION

 34 QUIZRR

(i) The directing power of electron donating group is generally in the following order.
Oă > NH2 > NR2 > OH > OMe, NHAC > Me > X
(ii) The directive power of electron withdrawing group is generally in the following order :
Me3N+ > NO2 > CN > SO3H > CHO >COMe > CO2H

Ex a m p l e 1 3
Arrange the following substances in order to activating a benzene ring.
Benzamide, Aniline, Acetanilide
Solution : O O

NH2 NH ă C ă CH3 C ă NH2

> >

In aniline, benzene ring is directly attached to ăNH2 which releases electrons by resonance effect,
where as the activation of ăNH2 group can be decreased by converting it to anilide and in amide, ring
is attached to electron withdrawing group which deactivates the ring.

3 .6 .4 U s e o f p r o t e c t i n g g r o u p
Groups like ăNH2 and ăOH activate the benzene ring to a great extent and cause undesirable
reactions e.g. nitration of aniline with nitric acid is not possible directly as nitric acid oxidizes and
destroys the highly activated ring. But its nitration can be carried out by use of protecting group as
follows : NH · COCH3 NHCOCH3 NHCOCH3
NH2

NO2
CH2COCl or HNO2
+
(CH3 CO)2 O

NO2

(i) H2 O/H2SO4/
(ii) OH ă

NH2 NH2

NO2
+

NO2

ELECTROPHILIC AROMATIC SUBSTITUTION

 QUIZRR 35

In the above reaction, a mixture of ortho and para substituted products is formed. If we desire
to form only ortho product then the para position is blocked with help of blocking reagents e.g. conc.
H2SO4 and tert butyl halides.

NH2 NHAC NHAC NHAC NH2

NO2 NO2
CH3COCl Conc. H4SO4 HNO3 (i) H2 O/H2 SO4/
(ii) OH ă

SO H SO H
3 3
P - position blocked

Please note that the blocking reagents are bulky, hence they do not form ortho substituted
product.
Thus they can be used to block p positions.

3 .6 .5 Ori e n t a t io n i n d i s u b s t i t u t e d B e n ze n e
Both the group present on ring collectively decide the position of incoming third group.
Case I : If both are electron donating group then position of incoming group is decided by the
group with more electron donating power.
Case II : If one group is eă donating and other is eă withdrawing, then position of incoming
group is governed by eă donating group.
Case III : When both are eă withdrawing groups, then position of incoming group is decided by
group which is more deactivating power. But it is difficult to introduce the incoming
group.

Ex a m p l e 1 6

CH3

Conc. OHNO3
?
Conc. H2SO4
NO2

Solution :
ăCH3 is eă donating and NO2 is eă withdrawing. Therefore incoming group position will be decided
by ă CH3.

ELECTROPHILIC AROMATIC SUBSTITUTION

 36 QUIZRR

Hence products are

CH3 CH3
O2N

NO2 NO2
NO2

Ex a m p l e 1 7
CN

Conc. H2SO4
?
Conc. HNO3

NO2
Solution :
Both are eă withdrawing group; CN being less withdrawing. Therefore ăNO2 will decide the
position of incoming group.
Hence product is CN
NO2

NO2

Case IV : All other things being equal, a third group is least likely to enter between two groups
in the meta position. This is the result of steric hindrance and increases in importance with the size
of the groups on the ring and with the size of attacking electrophile.
Example :
OCH3
least
most favoured
favoured attack
attack

SO3H

ELECTROPHILIC AROMATIC SUBSTITUTION

 QUIZRR 37

3 .6 .5 .1 Se l e c t i v e A d d i t io n
The selective addition for further substitution of disubstituted benzenes can usually be predicted
by looking at the cumulative effects of the substituents.
As a suggested method, look at each of the substituents, label their directing effects, then indicate
the sites where they would promote reactivity with small arrows. Some issues that can arises are shown
by the following worked examples :

CH o,p CH O
3 3
O O CCH3
|| ||
CH3COCCH3
all positions equal
AlCl3

CH3 o,p CH3

CH3 o,p CH3

Br
Br2
substituents reinforce
each other Fe

NO2 m NO2

OH o,p OH
Br
stronger activator Br2
controls Fe

CH3 o,p CH3

CH3 o,p CH3

NO2
activating effects similar, but HNO2
steric effects favour ortho to
the smaller methyl group H2 SO4

C(CH3 )3 o,p C(CH3 )3

ELECTROPHILIC AROMATIC SUBSTITUTION

 38 QUIZRR

Ex a m p l e 1 8
The alkylation of phenol and aniline with alkyl halide in presence of AlCl3 gives poor
yields. Explain.
Solution :
In presence of Lewis acid (e.g. AlCl3), the group (ăNH2 or ăOH) becomes electron withdrawing.

Ex a m p l e 1 9
What happens when p-xylene is treated with concentrated sulphuric acid and the resultant
product is fused with KOH ?
Solution :
CH3 CH3 CH3

SO3 H OH
conc. fusion
H2 SO4 with KOH

CH3 CH3 CH3

p-Xylene 2-5. Dimethyphenol

Ex a m p l e 2 0
Explain the product formation in following reaction.

O
Br2
?
Fe

Solution :
Br

O O
and

Br

The oxygen-containing ring can be viewed as an OR group and an R group attached to the
benzene ring. Although both groups are activating. The OR group is more strongly activating. So the
positions ortho and para so it will be faster than the bromination of benzene which requires a
catalyst.

ELECTROPHILIC AROMATIC SUBSTITUTION

 QUIZRR 39

Ex a m p l e 2 1
What happens when toluene reacts with Br2 in presence of light ?
Solution :

Br
CH3

+ Br2 hv + HBr, due benzyl free radical stability

3 .6 .6 M a k i n g Po l y s u b s t it u t e d B e n ze n e s
Since the position of electrophilic attack on a substituted benzene ring is controlled by the substituent
already present rather than the approaching electrophile, the order of events in the synthesis of
polysubstituted benzenes need careful planning to ensure success.
The two factors that need to be monitored are :
l regiochemistry (selective addition)
l reactivity (for example Friedel-Crafts reactions are limited to halobenzenes and activated
benzenes)
Tip : Students often get this concept of what component is in control confused. Try thinking about
it in terms of an aircraft (the E+) coming into land at an airport (the Ar-X)... it is the control tower
at the airport on the ground. (-X) that does the „directing‰ of which runway and which ramp the
aircraft should go to.
l Draw the target product and label the substituents with their directing effects
l Look at these directing effects to see which align to allow the introduction of the appropriate
group
l If there is a choice, introduce the more activating group first.... it will make the subsequent
reactions easier
l Remember that some functional groups can undergo reactions that changes their directing
effects
l Check the order of reactions for compatibility
Here are a couple of examples :
1. Here the nitro group could direct to bromine to the correct position
Therefore in planning the synthesis we should use the nitro group to introduce the bromine

Br o,p

NO2 m NO2

ELECTROPHILIC AROMATIC SUBSTITUTION

 40 QUIZRR

NO2 Br
Actual Synthesis :
HNO3 Br2
H2 SO4 Fe
NO2
2. Here neither group directs to the correct location of the other.
But since the carboxylate could be introduced by the oxidation of a methyl group, which
directs o, p- we can use the methyl to direct the nitro group to the correct position.

CO2 H m CH3 o,p CH3

NO2 m NO2 m

CH3 CH3 CH3

Actual Synthesis :

CH3Cl HNO3 [O]

AlCl3 H2SO4 KMnO4

NO2 NO2
Note that the oxidation has to be after the nitration to get the correct orientation and that the
Friedel-Crafts alkylation has to before the nitration since nitrobenzene is too deactivated to undergo
alkylation.

3 .6 .7 Ele c t ro p h i li c A r o m a t i c Su b s t it u t i o n o f Po l y c y c l i c A r o m a t i c s
l Polycyclic aromatics such as naphthalene, anthracene etc. react with similar reagents to
those used for benzene
l Typically they are more reactive than benzene
l Reactions are usually less selective than those of benzene and mixtures of products are often
obtained
E E
1
2
+
E

1 - or  ă substitution 2 - or  ă substitution

ELECTROPHILIC AROMATIC SUBSTITUTION

 QUIZRR 41

For example, the nitration of naphthalene proceeds to give mainly 1-nitronaphthalene.

NO2

HNO3
H2 SO4

napthalene

This selectivity can be rationalised by drawing the resonance structures for intermediates produced
by attack of the electrophile at the 1- and 2- positions. Attack at the 1-position gives an intermediate
that is represented by 7 resonance contributors of which 4 leaves the aromaticity of the other ring
intact. In contrast attack at the 2-positions gives an intermediate with 6 resonance contributors in
which only 2 have the aromaticity of the other ring intact.

Attack at position-1

E E E
1
2 +
+ +
E

+
(1) (2) (3)

E E E

+ +
(6) (5) (4)

E
structure 1, 2, 6 & 7 have
+ aromaticity of the other ring infact.

(7)

ELECTROPHILIC AROMATIC SUBSTITUTION

 42 QUIZRR

Attack at position-2
1 + E E E
2
E
+
+

(1) (2) (3)

E + E E

(6) (5) (4)

There are 6 resonating structure out of them only 2 have aromaticity of the other ring intact.
In anthracene, the electrophile attacks preferentially at the 9 or 10 positions since the arenium
ion formed by the electrophilic attack at any of these positions can have two intact benzene ring in its
canonical forms, while attack of electrophile at any other position (1 or 2) would give arenium ion
having a naphthalene ring in its canonical forms. The resonance energy of 2 benzene rings is more
than the resonance energy of a naphthalene ring.

1 9 8
7
2
(here position 1, 4, 5 and 8 are
3 6 identical, positions 2, 3, 6 and 7
4 10 5 are identical and positions 9 and
10 are same).

3 .6 .8 Ele c t r o p h i li c A r o m a t ic Su b s t i t u t i o n o f H e t e r o a r o m a t i c s
1. Aromatic compounds which contain heteroatoms (e.g. O, N, S) are called heteroa roma tics.
2. The presence of the heteroatom influences the reactivity compared to benzene.
3. The 5-membered ring heterocycles (furan, pyrrole, thiophene) are  -electron rich
aromatics (6  electrons over 5 atoms).
4. This makes them more reactive than benzene (since the aromatics the nucleophilic component
in these electrophilic substitution reactions)
5. For example furan is similar to an activated benzene like methoxybenzene
6. Pyridine is less reactive than benzene (more like nitrobenzene) due to the electronegativity
of N, it is described as a -electron deficient aromatic

ELECTROPHILIC AROMATIC SUBSTITUTION

 QUIZRR 43

7. The basic nature of the N atom of pyridine often interferes and interacts with the electrophile
E+ which further deactivates the system.
Compound Name Line Drawing 3D Model

Furan
O

Thiophene
S

Pyrrole
N

Pyridine
N
3 .6 .8 .1 Fi v e M e m b e r e d H e t e ro c y c l i c Ri n g
The 5 membered heterocycles react in a similar way. As an example here is the general pattern
for the electrophilic aromatic substitution reactivity of furan, complete with the 3 important resonance
structures that justify the reactivity of the 2-position.
+
E +

O O E
Mechanism :
+
+ E E E
E
+
O O H O H O H

H H

E E
3ăsubstitution:
+
+
N N

H H
(Stable contributorăoctet of
every atom is complete)

ELECTROPHILIC AROMATIC SUBSTITUTION

 44 QUIZRR

Furan and thiophen are also activated towards electrophiles and react predominantly at the 2-
position. Theory is similar to that for pyrrole, namely, that the heteroatom is able to delocalize the
positive charge on the transition state. Since oxygen accommodates a positive charge less readily than
nitrogen, furan is less reactive than pyrrole. Just as phenol is less reactive than aniline. The +M effect
of sulphur is smaller than that of oxygen because the overlap of the differently sized păorbitals of
carbon and sulphur is less than furan. Thus, the reactivity order of 5ămembered heterocyclics towards
electrophilic substitution would be
pyrrole > furan > thiophene

3 .6 .8 .2 Six -M e m b e r e d H e t e r o c y c l i c Ri n g s
The principles governing the reactivity of these compounds are illustrated by reference to pyridine.
The transition states for substitution at the 3ă and 4ăpositions can be represented as the hybrids.
H H H
+

E E E
3ăsubstitution:
+ +
N N N

H E H E H E

+ +
4ăsubstitution:
+
N N N

In each case, the positive charge is less well accommodated than in reactions on benzene because
nitrogen is more electronegative than carbon. Hence, both the 3ă and 4ăpositions are deactivated, the
latter more strongly because of the high energy of the contributing structure which contains divalent
positive nitrogen. The 2ăposition resembles the 4ăposition, as reference to the appropriate resonance
structures will show.

3 .6 .9 . Re a c t io n s o f B e n ze n e a n d I t s H o m o l o g u e s
(i) Benzene on vigorous oxidation (combustion) gives CO2 and H2O.

15
C6 H6 (l)  O2 (g)  6CO2 (g)  3H2O(l )
2
Benzene on oxidation by air at 723 K in presence of V2O5 gives maleic anhydride.
O
C
V2 O5 CH
+ 9 O2 O + 2H2O + 2CO2
2 at 723 K CH C
O
ELECTROPHILIC AROMATIC SUBSTITUTION
 QUIZRR 45

(ii) Side chain oxidation of alkyl benzenes

An alkyl benzenes (irrespective of the chain length) on oxidation by acidified or alkaline KMnO4
(followed by acidification) are degraded to benzoic acid provided they have a benzylic hydrogen.
CH3 CO2H

KMnO4, H +

CH2CH3 CO2 H

KMnO4, H +

H3 C CH3
CH CO2H

KMnO4, H +

CH2CH2CH2R CO2H

KMnO4, H +

Even if the side chain contains some functional groups, whether they are electron pushing or
electron withdrawing, are also degraded to benzoic acid on oxidation.

CH2CH2ăCHăCH3 CO2 H
·

NO2
KMnO4, H +

CH=CH2 CH=CH

and
are also oxidised by KMnO4, H+ or KMnO4, OHă to give benzoic

acid due to oxidative cleavage of C=C and ăC=Că

ELECTROPHILIC AROMATIC SUBSTITUTION

46 QUIZRR

Compounds that do not contain a benzylic hydrogen will not get oxidised to benzoic acid.
R

R·C·R

KMnO4, H +
No reaction

Compounds which contain, two alkyl carbons bearing benzylic hydrogen are oxidised to give two
ăCO2H groups on the benzene ring.

CH2 R CO2H
KMnO4, H +

CH2 R CO2H
Phthalic acid

CH2 R CO2H
KMnO4, H +

CH2 R CO2H
Isophthalic acid

CH2 R CO2H

KMnO4, H +

CH2 R CO2H
Terephthalic acid

CO2H
KMnO4, H +

CO2H

CO2H
KMnO4, H +

CO2H

ELECTROPHILIC AROMATIC SUBSTITUTION

 QUIZRR 47

(iii) Addition reactions :

Benzene is so stable that it gives addition reactions much less readily. It can be reduced by
catalytic hydrogenation, when three molecules of hydrogen add to it in presence of Pt as a
catalyst.

Pt
+ 3H2
423 K, 100 atm

Addition of 3 molecules of chlorine also takes place to one molecule of benzene in presence of
sunlight. The product formed is 1, 2, 3, 4, 5, 6ăhexachlorocyclohexane (also called as benzene
hexachloride). This compound is used as an important insecticide and is sold commercially in the
name of BHC or gammaxene.

Cl
Cl Cl
Sunlight
+ 3Cl2

Cl Cl
Cl

Ex a m p l e 2 2
Find the product

CH = CHCHO

KMnO4, H +
Product ?

Solution : COOH

ELECTROPHILIC AROMATIC SUBSTITUTION

 48 QUIZRR

M ISCEL LA N EOU S EX A M PLES

Ex a m p l e 1

CH3 · CH = CH2
A
HF or BF3

Identify A and also the electrophile involved in the reaction.

Solution :
+ +
H
CH3 · CH = CH2 CH3 · CH · CH3
CH3 · CH · CH3

+
CH3 · CH · CH3 +

(A)

is iso propyl benzene or cumene and electrophile involved is CH3 ă CH ă CH3 (isopropyl
carbocation). Rearrangements are also possible in Friedel Crafts reactions when benzene is treated with
n-butyl chloride and Lewis acid the product obtained is isobutyl benzene.

Ex a m p l e 2
Synthesize mănitroacetophenone from benzene.
Solution :
COCH3 COCH3

(CH2CO)2 O, anty AlCl2 conc. HNO3

F.C. alkylation conc. H2 SO4
NO2
Acetophenone

Ex a m p l e 3
In the following reaction,

O
conc. HNO3
X
conc. H2SO4
N

t h e st r u ct u r e of t h e m aj or pr odu ct ‘X’ i s

ELECTROPHILIC AROMATIC SUBSTITUTION

 QUIZRR 49

(a) (b) O2 N
O
NO2 O

N
N
H
H

(c) O (d) O

N N
O2 N
H H
NO2

Solution :
The ring to which ăNH group is attached is activated due to the lone-pair on N; while the ring
O
·

to which C is attached is deactivated. Hence, the electrophile would go to the para-position of the
·
·

activated ring.
 (b)

Ex a m p l e 4
Irradiation of an equimolar mixture of cyclohexane and PhCH3 gives mostly cyclohexyl
chloride with Cl2 and PhCH2Br with Br2. Explain.
Solution :
In these competitive reactions the reactivities of cyclohexane and toluene are compared ClĆ, being
more reactive and less reactive than BrĆ, reacts with the kind of H present in greatest number, which
in this case is one of the twelve equivalent HÊs of cyclohexane. The less reactive and more selective BrĆ
reacts with the most reactive H, in this case one of the three alkyl HÊs of PhCH3.

Ex a m p l e 5 O

Starting with benzene and succinic O anhydride synthesise -tetralone.

O O

ELECTROPHILIC AROMATIC SUBSTITUTION

 50 QUIZRR

Solution : O
O
C
AlCl3 CH2
+ O
FCR
CH2
O Zn ă Hg
C
conc. HCl
HO O SOCl2

CH2
AlCl3 CH2
FCR
CH2
O C
 ă tetralone Cl O

Ex a m p l e 6
Compound (A), B and (C) are three isomeric derivatives of benzene. Identify which is Oă,
mă or pă from the products of nitration ?
conc. HNO
A  3
two mononitro product
H 2SO 4

conc. HNO
B  3
three mononitro product
H 2SO4

conc. HNO
C  3
one mononitro product
H 2SO 4

Solution :
CH3 CH3 CH3

CH3 CH3 CH3

HNO3
(A) +
H2 SO4
NO2

NO2

CH3 CH3 CH3 CH3

NO2
HNO3
(B) + +
H2 SO4
CH3 CH3 CH3 O H CH3
2
NO2

ELECTROPHILIC AROMATIC SUBSTITUTION

 QUIZRR 51

CH3 CH3
NO2
HNO3
(C)
H2 SO4
CH3

CH3

Ex a m p l e 7
Write the structure of the major product (only mono-substitution is involved in each case).

F
CH2 ă Cl
+ AlCl3
?

Solution :
F

CH2 ă Ph

Ex a m p l e 8
Complete the following :

H3C
BF3
+ CH2 ? + HF
(a) (b) ?
H3C

C(CH3 )3

Br2 HNO3
(c) ? (d)
acetic acid
CH(CH3 )2

ELECTROPHILIC AROMATIC SUBSTITUTION

52 QUIZRR

OCH3
CF3

NH2 H2 SO4
Br2 + (CH3)2C = CH2 ?
(e) ? (f)

O2 N
CH3

Br2
(g) OH ?
CHCl3

Solution :

CH3 CH3

(a) CH3 (b)

C(CH3 )3
H Br

(c) (d)
CH(CH3 )2
H Br NO2

OCH3
C
CF
3
C(CH3)3
NH2
(e) (f)

O2 N Br
CH3

OH
(g)
Br

ELECTROPHILIC AROMATIC SUBSTITUTION