Page 1

ELECTROPHILIC SUBSTITUTION
Benzene nucleus is composed of six sp2 hybridised carbon atoms linked together to form a hexagonal
planar structure with one H atom bonded to each carbon. All the carbon atoms have one unhybridized
porbital with one electron, which forms a sextet cloud of electrons above and below the plane of the benzene
ring. It means that there is high density of electronic charge in benzene. Hence, a strong electrophile (electron
deficient group) can now attack this electron cloud i.e. benzene readily undergoes electrophilic substitution.
Electrophilic substitution in benzene ring is believed to be a bimolecular (S E2) reaction, which involves the
following pathways. As the electrophile comes closer to the benzene nucleus, a complex is formed.
complex rearranges to give complex.
H
electrophilic
attack

+ E

rearranges

complex

complex
(loose association)

complex formation results in the loss of aromaticity (breaking of the sextet) which is compensated by
resonance.
+
H
H
H
E
+
+ E
E
E
E
+ H+
+

+
Resonance stabilised

In the last step, intermediate carbonium ion, in the presence of a proton acceptor, loses a proton to give the
substituted product with complete sextet.Above E+ is an electrophile and may be X+ (Cl+, Br+, I+) in
halogenation, NO 2 in nitration, SO 3 in sulphonation and R + or RCO + in Friedel Crafts reaction.

MECHANISM OF ELECTROPHILIC AROMATIC SUBSTITUTION REACTIONS

Substitution reactions like halogenation, nitration, sulphonation, Friedel Crafts reactions have been referred to
as electrophilic aromatic substitution reactions. The mechanism of these reactions is described as below.

1.

NITRATION

Nitration is brought about by the action of concentrated nitric acid or a mixture of concentrated nitric acid and
sulphuric acid often called nitrating mixture. HNO 3 alone is a weak nitrating agent whereas the mixture is

strong nitrating mixture.The reaction involves electrophilic attack by the nitronium ion, NO 2 which is produced
under the conditions of reaction. When HNO 3 alone is the nitrating agent.HONO2 + HNO3

H2O +

NO 3 NO 2 when concentrated HNO 3 and concentrated H2SO4 is the nitrating mixture, NO 2 (Nitronium ion) is
produced as follows:
..
H2SO4
HONO2

H2ONO2

H2SO4

H3O + HSO4 + NO2

+
HSO4
i.e. HNO3 + 2H2SO4

NO2 + H3O + 2HSO4

when

HNO3

alone

is

the nitrating agent,

generation of water dilutes the acid and generation of NO 2 ion is slowed down. Hence it is a mild nitrating
agent.But when mixture of concentrated HNO 3 and concentrated H2SO4 is the nitrating agent. concentrated
sulphuric acid helps to speed up the generation of nitronium ion by absorbing water molecule and producing
H3O+ in the medium.Now, the NO 2 ion attacks the benzene nucleus and forms an intermediate cation, a
benzenonium ion, which loses a proton to yield the nitro derivative.

Page 2

+ NO2

nitronium ion

Electrophilic
attack

NO2

complex

NO2
H+

NO2

NO2

NO2 HSO 4

H+

Nitrobenzene

H2SO4The reaction by which nitronium ion is produced is simply an acid base equilibrium in which sulphuric
acid serves as the acid and the much weaker nitric acid serves as a base. The very strong acid, sulphuric acid

causes nitric acid to ionise in the sense, HO

NO2+, rather than in the usual way, H+

ONO2. The

nitronium ion is well known existing in salts such as NO 2 ClO 4 and NO 2BF4 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 rate than can be explained on the basis of the
concentration of

NO2 that is present in the mixture. This has been shown to be due to the presence of nitrous

acid in the system which nitrosates the reactive nucleus via the nitrosonium ion,
HNO2 + 2HNO3
H3O + 2NO3 + NO

OH

OH

NO

NO3

2.

OH

NO .

OH
HNO3

+ HNO2

NO

NO

NO2

SULPHONATION

Sulphonation is done by heating the substrate with conc. sulphuric acid or fuming sulphuric acid containing
varying proportions of sulphur trioxide.Experimental work based on kinetic studies in concentrated sulphuric
acid and in oleum (H2 SO4 , SO3) strongly favours the theory that sulphur trioxide is the active species. SO 3 is
bonded to three more electronegativity oxygen atoms. Hence S is electron difficient centre acting as
electrophile.

S
O

S
O

S
O

S
O

Now the electrophilic reagent, SO 3, attacks the benzene ring to form the intermediate carbocation.
SO3 + H3 O+ + HSO 4

2H2SO4

+
O

SO3

SO3

SO3H Sulphonation, like

SO3

iodination, is reversible and is believed to take place in concentrated sulphuric acid via the pathway,

Page 3

SO3

H
k1

+ SO3

k2

k1

SO3

SO3H
+H

fast

In oleum, the complex is believed to undergo protonation of the SO 3 before undergoing CH fission
to yield the SO 3H analogue. Like iodination, sulphonation exhibits a kinetic isotope effect, indicating that CH
bondbreaking is involved in the ratelimiting step of the reaction, i.e. that k1 ~
> k2 .

3.

HALOGENATION

In halogenation, electrophiles are Cl+, Br+ and I+. As halogens are neutral (nonpolar) covalent molecules, so
to
generate
polarity
these
react
with
halogen
carriers
i.e.
Lewis
acids
(transition metal halides). The Lewis acids polarizes the halogen molecule forming complexes with negative
ion, leaving positive ion to react with benzene nucleus. The positively charged or electrophile species then
attacks the nucleophilic aromatic substrate to give an intermediate carbonium ion which is resonance
stabilized. It abstracts a proton and electron pair binding the hydrogen to the ring moves to restore the highly
stable benzene ring system.

(i) FeCl3 + Cl2 Cl

H
+

(ii)

Cl+

FeCl3 Cl+ + FeCl4

Cl

H
Cl

H
Cl

H
Cl

+
+

(iii) FeCl 4 H FeCl 3 HCl orFeCl 3 + Cl 2 Cl

+

+ Cl

Cl

H
Cl

Cl+

FeCl3

Cl

Cl

FeCl

FeCl3

H
Cl + FeCl 4

H
Cl
+

Cl
+ H+

Cl
+ H+
FeCl 4 + H+ FeCl3 + HCl

Role of Lewis acid

The loosely held electrons of the double bond in alkenes polarize the halogen molecule even in the absence
of
a
Lewis
acid
catalyst.
The

electrons
cloud
in
benzene
is
relatively
less available and consequently the presence of a Lewis acid catalyst is necessary to polarize the halogen
molecule,
at
least
in
the
case
of
less
reactive
aromatic
compounds
(benzene, chlorobenzene etc.). The fact that halogenation of more reactive aromatic compounds (phenol,
aniline etc.) where electrons are more available proceeds smoothly even in the absence of Lewis acid
catalyst establishes the role of Lewis acid in the above mechanism for halogenation of aromatic
compounds.Note: A similar dual mechanism can also operate when halogenation is carried out with
hypochlorous or hypobromous acid. This reaction is acid catalyased. HOCl + H+
H2O+Cl

Page 4

+ H2O Cl
+

H2O

Cl

Cl

H
Cl

Cl
+ H+

Instead of a protonated hypohalous acid, the attacking reagent can be a positive halogen cation,
without affecting the course of reaction.H2O+Cl
H2 O + Cl+. Kinetic isotope effects have not been
observed for chlorination and only rarely for bromination, i.e. the reactions normally follow pathway like
nitration. In iodination, which only takes place with iodine itself on activated species, kinetic isotope effects are
the rule. This presumably arises because the reaction is readily reversible (unlike other halogenations), loss of
I occurring more often from the complex than loss of H, i.e. k1 ~
> k2.

OH

OH
k1

+ I2

k 1

OH
I

k2

+ HI

I
H I
Thus kH/kD for the iodination of phenol and 2, 4, 6trideuteriophenol is found to be 4. Iodination is
often assisted by the presence of bases or of oxidising agents, which remove HI and thus displace the above

equilibrium to the right. Oxidising agents also tend to produce I , or a complex containing positively polarized
iodine, from I2, thus providing a more effective electrophile. Halogenation may also be carried out by use of
+

interhalogen compounds BrCl, ICl,etc., attack occurring through the less electronegative halogen as this will
constitute the electrophilic end of the molecule.

4.

FRIEDEL CRAFTS REACTON

Alkylation or acylation of aromatic ring with alkyl halides or acyl halides in presence of a Lewis acid,
generally anhydrous AlCl3 (Friedel craft catalyst) is called Friedel crafts reaction.The aromatic ring, to which
the side chain is attached, may be that of benzene itself, certain substituted benzenes or more complicated
aromatic ring systems like naphthalene and anthracene. e.g.

R
+ HX

RX / AlX3

where X = Cl, Br, I, but the most effective catalyst is anhydrous AlCl3: R = CH3 , CH3 CH2 ,
O
O
C6H5 CH2 substituted alkyl groups, or acyl group CH3C or C6H5C etc. Because of low reactivity of
halogen attached to an aromatic ring, aryl halides cannot be used, in place of alkyl halides. Also, vinyl halides
cannot be used in stead of alkyl halides.
MECHANISM
It has been observed that rate of reaction [substrate] [RX] [AlX3]. It means the reaction is 3rd order,
which suggests that AlX3 is involved in the formation of transition complex.

4.1

ALKYLATION
+

The carbon atom of alkyl halides, R X, is electrophile, but rarely is it sufficiently effective so, to affect
the substitution of aromatic species. So, the presence of a Lewis acid catalyst is also required. Anhydrous
aluminium chloride, AlCl3, being a Lewis acid, accepts a lone pair of electrons from halogen (Chlorine atom) of
..
R Cl:
.. . This makes R (alkyl) group to be sufficiently polar so as to act as an electrophile. Now, two
mechanisms are possible for Friedel Crafts alkylation. Both involve electrophilic substitution, but they differ as
to the nature of the electrophile. One of the mechanism for Friedel Crafts reaction involves the following steps.

..
R

Cl:
(i)
.. + AlCl3

Cl

AlCl3 R+ + AlCl 4
Carbocation

Page 5

(ii)

+ R

complex

R
(iii)

AlCl4

+ HCl + AlCl3

In the above mechanism, the electrophile is a carbocation. The function of the aluminium chloride is to
generate this carbocation by abstracting the halogen from alkyl halide.On the other hand, the another
mechanism
is
carried
out
by
the
electrophile
which
is
an acid base complex of alkyl halide and Lewis acid, from which the alkyl group is transferred in one step from
halogen to the aromatic ring.
+

..
(i) R Cl:
.. + AlCl3
+

+ R

(ii)

AlCl3 .

Cl

Cl

H +AlCl4

AlCl3

complex

R
(iii)

H+

R
+ AlCl3 + HCl

AlCl4
Product

(i) Nature of alkyl groups

If the alkyl group is simple CH3 or CH3CH2, then a complex between alkyl halide and Lewis acid is
the electrophile as shown in second mechanism. But because of the relative stability of s and t carbonium
ions, the adducts with s ant t alkyl halides ionise and it is now the carbonium ion that is predominantly the

active species. e.g.Me3CCl + AlCl3 Me3C + AlCl 4

(ii) Temperature
Not only nature of the alkyl group, but also temperature determines the nature of electrophile. e.g.
nalkyl group can be introduced to a fair extent without rearrangement at low temperatures, because ionisation
of the adduct is retarded. But at higher temperatures, carbonium ion is formed which rearranges and the
product is rearranged alkyl benzene. Thus npropylchloride gives isopropyl benzene.
..

CH3CH2CH2Cl:
.. + AlCl3

(ii)

(i)
+

CH3CH2CH2

AlCl4
CH3CHCH2 +
rearranged

Cl

AlCl3

CH3CHCH3
2 Carbocation (more stable)

CH2CH2CH3 + AlCl3 + HCl

CH3
CH

npropyl benzene

CH3 + HCl + AlCl3

Isopropyl benzene

In the same way, isobutyl chloride gives tbutyl benzene.(iii)

Nature of Lewis acid as catalyst

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

AlCl3 > FeCl3 > BF3 > TiCl3 > ZnCl2 > SnCl4
The action of Me3CCH2Cl/AlCl3 on benzene is found to yield almost completely the rearranged product,
PhCMe2CH2Me, which can be explained on the basis of the initial electrophilic complex being polarized
enough to allow the rearrangement of [Me3CCH2 ]+ClAlCl3 to the more stable [Me2CCH2Me]+
ClAlCl3. By contrast Me3CCH2Cl/FeCl3 on benzene is found to yield almost completely the

Page 6

unrearranged product, Me3 CCH2Ph. This is due to the fact that the complex with the weaker Lewis acid, FeCl 3,
is not now polarized enough to allow of rearrangement.

4.2

ACYLATION

Acylation of benzene may be brought about with acid chlorides or anhydrides in presence of Lewis acids. e.g.
+ CH3COCl

COCH3
+ HCl

AlCl3

Acetophenone

Mechanism:
Friedel crafts acylation is found to follow the same general rate law as alkylation Rate [Substrate]
[RCOCl] [AlX3 ]In case of acylation, the nature of electrophile will be as follows:

..
(i) R C Cl:
.. + AlCl3

R C = O +AlCl4

AlCl3

R C Cl

(ii) R C Cl + AlCl3

..
(iii) R C Cl:
.. + AlCl3

R C Cl

AlCl3

Due to the presence of lone pair of electron on both chlorine and oxygen two intermediates are
possible and both are capable of electrophilic attack on benzene.
Acylium ions have been detected in a number of solid complexes, in the liquid complex between
CH3COCl and AlCl3 (by spectroscopy), in solution in polar solvents and in a number of cases where R is very
bulky. In less polar solvents the polarized complex R

AlCl3 has been detected to act as the

Cl
electrophile. Direct chemical evidence clearly indicates that both can be involved depending upon the
circumstances.Mechanism may be represented as follows:
O
+

(i) R C Cl + AlCl3

or

R C = O +AlCl 4

AlCl3

R C Cl + AlCl3

RC

Cl

AlCl3

AlCl3

R
Cl

Cl

(ii)
O

O + AlCl4

AlCl4
COR
+ AlCl3 + HCl
Product

Page 7

Comparison between alkylation and acylation

(i) A comparison of the electrophilic nature of both alkyl and acyl group indicates
acyl group is a better electrophile on account of two electron withdrawing atoms attached to C.

that

Cl

Cl

H
alkyl halide

Effective +ve charge density

on carbonyl carbon 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)

H3CC
COCH3
+

AlCl3

AlCl3

and is removed from further participation in the reaction.

(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, as in alkylation, but decarbonylation can take place,
especially where R would form a stable carbonium ion, so that the end result is then alkylation rather
than the expected acylation.

Me3C C = O CO + Me3C

CMe3
+ Me3C+

5. DIRECTIVE INFLUENCE OF SUBSTITUTENTS IN BENZENE

NUCLEUS
The first substituent may occupy any position in benzene ring i.e. one and only one monosubstituted
benzene
is
obtained.
The
next
group
may
go
to
ortho,
meta
or
para
position.
It is the group already present in the benzene nucleus that determines low readily the attack occurs and at
what position of the ring it occurs. In other words, the group attached to the ring not only affects the reactivity
but also determines the orientation of substitution. This is called directive influence of substituents in benz ene
nucleus. The substituent group is able to activate or deactivate the ring due to a number of factors like
inductive effect, electromeric effect, resonance effect and hyperconjugative effect. Depending on their directive
influence the substituent groups, except halogens, are divided into two different classes:
Class I : R, OH, OR, NH2, NHR, NR2, NHCOCH3, OCOCH3, Cl, Br, I, F, CH2 Cl, SH,
Ph, etc. These groups direct the incoming electrophile mainly to the o/ppositions.

Class II : NO2, CHO, CO 2 H, COCl, CONH2 , CO2R, SO3 H, SO2Cl, COCH3, CN, CCl3, NH3, NR3, OR2
etc. These groups direct the incoming electrophile mainly to the m position.

5.1

ACTIVATING GROUPS OR ELECTRON RELEASING GROUPS

All groups having one or more lone pair of electrons are activating groups because they release
electrons towards the nucleus increasing electron density and hence energy of the system. Reaction rate is
increased due to low energy of activation. Examples:

decreasing o & pdirecting strength

.. ..
..
..
..
..
..
O:
.. , NH2, NHR, NR2, OH,
.. OR, NHCOR, R, Ar, X:
..

Page 8

Activating groups make the electrons more readily available to an attacking electrophile by increasing
the electron density at o & ppositions and the product is always a mixture of
o & p isomers.
From an examination of the electronic structure and polar characteristics of o and
p directing groups, it is evident that with the exception of alkyl groups all of them possess at least one lone
pair of electrons at the atom adjacent to the benzene ring known as key atom. Also that their polar
characteristics are I effect and + R types, except alkyl group which is + I type and halogens which have strong
+ E effect in addition.
This lone pair of electrons is in conjugation with the electrons of the ring and exhibits a strong +R
effect, thus increasing the over all electron density in the benzene ring. Although the
I effect opposes the +R effect but latter predominates. Such groups. e.g. OH, OR, NH2, NHR, NR2 etc.
activate the benzene ring towards electrophilic substitution. However the relative increase of electron density is
great at o & p position and due to the nature of conjugation and hence the substitution occurs at these
positions.
Examples:
5.1.1

Let us consider monosubstituted benzene, C 6 H5S where S is a substituent.

WHEN THE SUBSTITUENT(S) IS ELECTRONDONATING

When the substituent S present in the ring, has one or more lone pairs of electrons on the atom
adjacent to the ring, it interacts with electron system of the ring. This gives rise to the following five
resonance forms.
+

:S

..

:
..

III

II

IV

Resonance
Hybrid

The structure of the monosubstituted benzene, C 6H5 S , is in fact represented by the resonance hybrid.
In the hybrid structure the overall electron density of the benzene ring is enhanced compared to unsubstituted
benzene ring and more so at the o & p positions of the ring. Therefore the presence of an electron donating

group such as S causes further electrophilic substitution in o & p positions and also activates the ring to
electrophilic attack.

Let us take the example of phenol, C 6H5 O

H, and aniline C 6H5 NH2 , which have available

electron pair on the key atoms of the substituents. Thus phenol and aniline exhibit resonance and can be
represented as hybrid of the fine canonical forms.

..
:OH

..

+ OH

..

..

..

:
..

III

II
+

:NH2

NH2

NH2

..

II

..
:OH

+ OH

+ OH

..

III

NH2

..

+ :OH

IV
:NH2

Resonance
Hybrid

NH2

IV

Resonance
Hybrid

Page 9

The overall electron density of the ring in each hybrid is increased and the benzene ring system as a
whole is activated to electrophilic attack. Of course, the electrophile (E +] would attack the ring preferentially at
o and p positions where the electron density is relatively greater as compared to the meta positions.

Thus, all the groups which are electron donating O H , O R , N H 2 , NHR, NR2, NR3, etc. are orthopara

directing and facilitate electrophilic substitution in the benzene ring.

5.1.2

EFFECT OF ALKYL GROUP AS A SUBSTITUENT

Since alkyl group has no lone pair of electrons on key atom i.e. carbon atom, yet it is o & p directing.
First
it
is
because
of
the
fact,
that
alkyl
group
releases
electron
due
to
its
+I (inductive) effect and hence tends to stabilise the carbocation by dispersal of its positive charge.Secondly it
is because the group electronegativity of methyl group is less than that of phenol group. At the same time, c of
methyl group is sp3 hybridised whereas that of phenyl group is sp2 hybridised. So due to greater scharacter
of carbon atom of phenyl group, electron is withdrawn towards benzene ring. Third, methyl group repels
electrons towards the ring by hyperconjugation.

H
H C H+

H
HCH

H
H C H+

H
H C H+

H
HCH

All the nine hyperconjugative resonating structures reveal that electron density is enhanced (i.e. ve
charge is developed) at o & p positions simultaneously. Therefore, further electrophilic substitution occurs at
these positions.The electrophilic substitution of tert butyl benzene yields almost exclusively the para isomer.
This is so because the electrophile approach to the ortho position is impossible on account of the steric
influence of the substituent C(CH3 )3.

CH3

CH3

H3C C CH3
+ NO 2

H3C C CH3
Nitration

tertbutyl benzene

H+

NO2

It has been observed that the larger the size of the alkyl group already present, the smaller is the amount of
the o isomer formed in an aromatic electrophilic substitution reaction. In other words, the bulky alkyl groups
lead
to
steric
hindrance
to
the
introduction
of
new
substituents
in
o positions.
5.1.3

EFFECT OF HALOGENS

Halogens are unusual in their effect on electrophilic aromatic substitution. They are deactivating yet ortho, para
directing.A halogen substituted benzene (C 6H5X) by virtue of the presence of unshared electron pair on the
halogen, exhibits resonance. Thus it can be represented by the resonance hybrid of the following canonical
forms:

..
:X:

..
+:X

..
+:X

..

..
+:X

..
:X:
..

..

Halogens withdraw electrons through its inductive effect (I) and releases electrons through it
resonance or mesomeric effect (+M). Thus for halogen, the two effects are more evenly balanced and we
observe the operation of both.
Through its inductive effect halogen tends to withdraw electrons and thus destabilise the intermediate
carbocation. This effect is felt for attack at all positions, but particularly for attack at the positions ortho and
para to the halogen.

Page 10

Through its resonance effect halogen, tends to release electrons. This electron release is effective only
for attack at the positions ortho and para to the halogen. The combination of the two effects makes the
halogenated benzene deactivated. This is so because the inductive effect is stronger than the resonance
effect. Thus halogen, though, o and p directing, yet deactivates the benzene ring.

5.2

DEACTIVATING GROUP OR ELECTRON WITHDRAWING GROUP OR META DIRECTORS

Such groups have tendency to withdraw electrons from the benzene nucleus and thus decreasing its
electron density are known as deactivating groups.
Due to decrease in electron density of the ring, the rate of electrophilic substitution is retarded. Thats
why these group are called deactivating group.
A look on the resonating structure reveal that these groups develop positive charge at ortho and para
positions leaving the metapositions as the point of relatively high electron density and hence the electrophilic
substitution occurs at mposition, not at o and ppositions. Deactivating groups have bonds with one more
electronegative atom.
Examples:

O
O
O
O
O
O
O
+
NR3, N
, CN, SOH, CH, CR, COH, COR, CNH2, NH3
O
O
+

decreasing meta directing strength

Predict the reactivity and orientation in (a) PhN=O and (b) PhS+Me2.
ELECTRONIC EXPLANATION OF mDIRECTIVE INFLUENCE

The polar characteristic of these groups is I and R with the exception of NR 3 and CCl3 groups

which exhibit only I effect. Hence NR 3 and CCl3 groups deactivate the benzene ring in general by
decreasing electron density due to I effect. However, the withdrawal of electron from ortho and para positions
is as compared to mposition. Thus, meta position remains the point of comparatively high elec tron density
and electrophilic substitution occurs preferentially at metaposition.
Examples:
(i) When the substituent has at least one strongly electronegative atom and a multiple bond in conjugation
with benzene ring:
Let A = B represents the group in which B is more electronegative than A. The highly electronegative
atom pulls the electron pair of the multiple bond which in turn withdraws electrons from benzene ring (
M effect) giving rise to the following five canonical forms:

..
..
..
A =B
A B
A B
A B
A B
A =B

II

IV

III

Resonance
Hybrid

The structure of the benzene derivative C 6 H5A = B is, in fact, represented by the resonance hybrid
shown above. Evidently electrons are withdrawn by the substituent group from the ring and more so
from the o p positions where the electron density declines. Also, the meta positions have relatively
more electron density and therefore electrophile substitution take place at the meta positions.
The nitro and sulphonic acid groups offer examples of the type of electron withdrawing substituents
which are characterized by the presence of a strongly electronegative atom attached to another more
electronegative atom by a multiple bond.
ortho, para
VSA

SA

meta
A

SD

VSD

Page 11

OH, NH2,

NHCOR,

NHR, NR2

OCOR, OR

R, Ar
C

I, Br, Cl,

SO3H, CN, CHO

NO2, CF 3,

F, CH2X

COR

NR 3

COOH, COOR,
COCl

S , NO

Rank each of these species in order of decreasing reactivity to electrophilic substitution:

PhMe, PhNMe2, PhN+Me3, PhCH2N+Me3.

5.3

ORIENTATION IN BENZENE RING WITH TWO SUBSTITUENTS

The position taken up by a third electrophile entering the ring depends on the nature of the two groups
already present. It is often possible in such cases to predict the correct isomer; but remember following
generalizations in order to do so.
1. When the two groups direct differently, i.e. they belong to the classes
class I group takes precedence.

I and II, then

In the following examples, the number of arrowheads indicates (qualitatively) the amount of substitution
and the encircled number below indicates the number of isomers.
For example,
Cl

OH
NO2
NO2
3

2. When both groups belong to class I, then introduction of third group is very easy and
the group enters in accordance with higher activating group. For this purpose, we can
arrange the groups in the following order: NH2, OH, NR2, O > OR, OCOR, NHCOR
> R, Ar > halogen. For example,

OH

Cl
1

3. When both groups belong to class II, then it is difficult to introduce a third group and the deactivating
power of groups is in the order:
Me3N+ > NO2 > CN > SO3H > CHO > COMe > CO 2H
The more deactivating group controls the orientation because the arenium ion formed will be less
destabilized. For example,
NO2

NO2
CHO

CHO
1

Page 12

4. 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 the attacking electrophile. For example,

OCH3

Most favoured
attack

Least favoured
attack

SO3H
3

Now, using these generalizations, we can predict the preferable attack by the incoming group in
disubstituted benzene. We can have following possibilities:
(a) When the two groups present are such that they belong to different categories and oppose each other.
For example, in mhydroxy benzaldehyde, the incoming electrophile is oriented by OH group (and not
by CHO group). As OH group is o/pdirecting, thus attack of the electrophile can take place at three
sites. Attack at position2 is least favoured according to rule 3, but attack at position4 is the most
preferred.

OH
3

4
1

5
6

CHO

(b) When the two groups present are such that they belong to different categories but they reinforce each
other,
then
the
third
group
enters
almost
entirely
at
one
position.
For example, the incoming group in pchlorobenzoic acid goes to the position ortho to the chloro group
and meta to the carboxyl group.
CO2H

Cl
1

Some other examples are:

Me

OH

OH
NO2

NO2
1

NO2
1

(c) When the two groups belong to category I (having large difference in their activating ability) and are
placed such that they oppose each other, then the third group enters in accordance with the group
having higher activating ability.
For example, in ocresol (omethyl phenol), the incoming electrophile could go at position4 and 6 but
attack at position4 is greatly favoured due to less steric repulsion.

Page 13

OH
1

CH3

5
4

(d) When the two groups belong to category I and are placed such that they reinforce each other, the
incoming electrophile enters almost entirely at one position. For example, 1,3dimethylbenzene is
substituted at the position4 (ortho to one CH3 group and para to the other CH3 group), but not at the
position5 (meta to both) because of rule 4.

CH3
1

6
3

CH3

(e) When the groups are such that they belong to category I with almost identical directing abilities and
oppose each other, then predictions are more difficult. In a case such as,
OCH3
NHCOCH3

where two groups of about equal directing ability are in competing positions, all four products can be
expected and it is not easy to predict the proportions, except that steric hindrance should probably
reduce the yield of substitution ortho to the acetamido group, especially for large electrophiles. Mixtures
of about equal proportions are obtained in such cases.
Few other examples are

Me

Me

NH2

Cl

OH

Br

Cl

Cl
2

(f) When the groups are such that they belong to category I with almost identical directing ability and they
reinforce each other, then also the predictions are difficult.
For example, in mmethoxy acetamide, the attack at position2 is least favoured according to rule 4
but attack at position4 and at 6 is equally feasible.
NHCOCH3
1

6
3

5
4

OCH3

(g) When both the groups belong to class II and are present such that they oppose each other, then the
more
deactivating
group
decides
the
orientation
of
incoming
electrophile.
For example, in onitro benzaldehyde, the incoming group attacks at position3 and at position5, of
which position5 is more favoured because of lesser steric repulsion.

Page 14

CHO
1

NO2

(h) When both the groups belong to class II and are present such that they reinforce each other, then
attack takes place entirely at one position.
For example,
the groups.

3nitro

benzaldehyde

is

substituted

at

position5

as

it

is

meta

to

both

NO2
3
2

4
5
1
6

CHO

6.

SUBSTITUTION IN OTHER AROMATIC SYSTEMS

6.1 NAPHTHALENE AND ANTHRACENE RINGS

The delocalization of the positive charge in the transition states of electrophilic substitutions is
increased by the fusion of two or more benzene rings and the polycyclic hydrocarbons are therefore all more
reactive than benzene.
Substitution in naphthalene is illustrative. The transition states for the reaction at 1 and 2positions
may be represented as follows:

H E

H E

H E

1substitution:

H E

H E

2substitution:

H
E

H
E

H
E

H
E

In each of the two transition states, the positive charge is more extensively delocalized than in reaction
with benzene, leading to lower activation energies. Further, the three starred structures are of benzenoid type
and therefore of lower energy content than the remainder in which the benzenoid nature of the second ring has
been destroyed. Since there are two such lowenergy contributors for 1substitution as compared with one for
2substitution, it is understandable that the 1position should be the more reactive than 2position.
The presence of an electronattracting group in naphthalene reduces the reactivity and causes
substitution to occur in the unsubstituted ring, mainly at the 5 and 8positions (i.e. the two 1positions of that
ring). An electronreleasing group activates the molecule further and reaction occurs in the substituted ring. If
the group is in the 1position, substitution occurs at the 2 and 4positions (i.e. ortho and para to the
electronreleasing group), but a 2substituent directs almost entirely to the 1position, although the 3position

Page 15

is also an ortho position. The reason is that the stabilization of the transition state which is provided by the
substituent
is
more
effective
when
the appropriate resonance structure is benzenoid (1substitution) than when it is not (3substitution). For
instance,
H E

OH
OH
..
..
*

H
(Nonbenzenoid)

(Benzenoid)

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 rings 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

7
6

3
10

(Position 1,4,5 and 8 are identical, positions 2,3,6 and

7 are also identical and positions 9 and 10 are same)

6.2 FIVEMEMBERED HETEROCYCLIC RINGS

The principles that govern the electrophilic substitutions of this group of heteroaromatic compounds will
be illustrated by reference to pyrrole.
Pyrrole is highly reactive at both the 2 and 3positions. The reason is that the transition state for
substitution at each position is strongly stabilized by the accommodation of the positive charge by
nitrogen, in just the way that aniline owes its reactivity to the exocyclic nitrogen. 2substitution
predominates because the positive charge in the transition state is delocalized over a total of three
atoms, compared with two for 3substitution.
The similarity of pyrrole
at all its activated
2,4,6tribromoaniline. In
be compared with the
benzenoid compounds.
catalyst.

and aniline is particularly apparent in their reactions with bromine: each reacts
carbon atoms, pyrrole giving tetrabromopyrrole and aniline giving
fact, pyrrole is even more strongly activated than aniline and should perhaps
phenoxide ion: each undergoes the ReimerTiemann reaction, unlike other
In addition, pyrrole undergoes FriedelCrafts acylation in the absence of a

2substitution:

..

H
E

N
H

..

H
E

H
E

H
(Stable contributoroctet of
every atom is complete)

H
E

3substitution:

..

N
H

N
H
(Stable contributoroctet of
every atom is complete)

Furan and thiophen are also activated towards electrophiles and react predominantly at the 2position.
The underlying theory is similar to that for pyrrole, namely, that the heteroatom is able to delocalize the

Page 16

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 porbitals of carbon
and sulphur is less than in the case of carbon and oxygen so that, understandably, thiophen is less
reactive than furan. Thus, the reactivity order of 5membered heterocyclics towards electrophilic
substitution would be
pyrrole > furan > thiophene.

6.3 SIXMEMBERED HETEROCYCLIC RINGS

The principles governing the reactivity of these compounds are illustrated by reference to pyridine. The
transition states for substitution at the 3 and 4positions can be represented as the hybrids.
H
H
H

E
E
E
3substitution:

H E

N
H E

H E

4substitution:
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 3 and 4positions are deactivated, the
latter more strongly because of the high energy of the contributing structure which contains divalent
positive
nitrogen.
The
2position
resembles
the 4position, as reference to the appropriate resonance structures will show.

REACTIONS OF BENZENE AND ITS HOMOLOGUES

(i) Benzene on vigorous oxidation (combustion) gives CO 2 and H2O.
15
O 2 (g) 6CO2(g) + 3H2 O(l)
C6H6 (l) +
2
Benzene on oxidation by air at 723 K in presence of V2O5 gives maleic anhydride.

O
+

9
O2
2

V2O5
at 723 K

CH

CH C

O + 2H2O + 2CO2

O
(ii) Side chain oxidation of alkyl benzenes
All alkyl benzenes (irrespective of the chain length) on oxidation by acidified or alkaline KMnO 4
(followed by acidification) are degraded to benzoic acid provided they have a benzylic hydrogen.

CO2H

CH3
KMnO4, H+

CO2H

CH2CH3
KMnO4, H+

H3C

CH3
CH

CO2H
KMnO4, H+

Page 17

CO2H

CH2CH2CH2R
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.

CH2CH2CHCH3
NO2

CO2H

KMnO4, H+

CCH

CH=CH2

are also oxidised by KMnO 4, H+ or KMnO 4, OH to give benzoic acid due to

and
oxidative cleavage of

C=C and CC.

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

R
RCR
KMnO4, H+

No reaction

Compounds which contain, two alkyl carbons bearing benzylic hydrogen are oxidised to give two CO2H
groups on the bezene ring.

CH2R

KMnO4, H+

CO2H

CH2R

CO2H
Phthalic acid

CH2R

KMnO4, H+

CH2R

CO2H

CO2H
Isophthalic acid

CH2R

CO2H
+

KMnO4, H

CH2R

CO2H
Terephthalic acid
KMnO4, H+

CO2H
CO2H

KMnO4, H+

CO2H
CO2H

(iii) Addition reactions:

Page 18

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.

+ 3H2

Pt
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
1,2,3,4,5,6hexachlorocyclohexane
(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
+ 3Cl2

Sunlight

Cl

Cl

Cl

Cl
Cl

PROFICIENCY TEST
The following 10 questions deal with the basic concepts of this section. Answer the following briefly. Go
to
the
next
section
only
if
your
score
is
greater
than
or
equal
to
8.
Do not consult the study material while attempting the questions.
1.

True/False. An electron donating substituent in benzene orients the incoming electrophilic group to the
meta position.

2.

True/False. The electrophile in the sulphonation of aromatic molecule may be either SO 3 or HSO 3 .

3.
4.
5.

True/False.
True/False.
True/False.
in benzene,

6.
7.

True/False. An activating group activates only ortho and para positions in benzene ring.
True/False. Benzene in the presence of AlCl3 reacts with isobutyl bromide to give tertbutylbenzene.

8.
9.

True/False. The monobromination of acetanilide proceeds slower than benzene.

True/False. A tribromobenzene gives two isomers when it is mononitrated. The compound is 1, 2,
4tribromobenzene.
True/False. Monobromination of ptoluenesulphonic acid followed by treatment with acid and
superheated steam gives mbromotoluene.

10.

In FriedelCrafts alkylation the electrophile is a carbocation.

In FriedelCrafts alkylation, AlCl3 acts as a Lewis base.
A substituent, which stabilises the intermediate carbocation in the electrophilic substitution
activates the latter.

ANSWERS TO PROFICIENCY TEST

1.

False

2.

True

3.

True

4.

False

5.

True

6.

False

7.

True

Page 19

8.

False

9.

False

10.

False

SOLVED OBJECTIVE EXAMPLES

Example 1:
In the following reaction,
O

conc. HNO3
conc. H2SO4

N
H

the structure of the major product X is

O

(a)

NO2

N
H

(c)
N
H

(b)

O
N
H

(d)
NO2

O2N

O
O2N

N
H

Solution:
O

The ring to which NH group is attached is activated due to the lone-pair on N; while the ring to which
attached is deactivated. Hence, the electrophile would go to the para -position of the activated ring.

is

(b)

SOLVED SUBJECTIVE EXAMPLES

Example 1:
Compare the products of the reactions of PhCH 2CH3 with Br 2 and Cl2 in light and explain any differences.

Solution:
Bromination gives bromoethylbenzene exclusively. The 2 benzylic position is only slightly favored over the 1
alkyl position in chlorination, the products being PhCHClCH3 (56%) and PhCH2CH2Cl (44%). The less reactive Br
is more selective than the Cl, which abstracts an H in a more random fashion (ReactivitySelectivity principle).

Example 2:
Irradiation of an equimolar mixture of cyclohexane and PhCH 3 gives mostly cyclohexyl chloride with Cl 2
and PhCH2Br with Br 2. Explain.

Solution:
In these competitive reactions the reactivities of cyclohexane and toluene are compared, Cl , being more reactive
and less selective than Br , reacts with the kind of H present in greatest number, which in this case is one of the
twelve equivalent Hs of cyclohexane. The less reactive and more selective Br reacts with the most reactive H, in
this case one of the three alkyl Hs of PhCH3.

Example 3:
Deduce the structure of compound A, C 9H8, from the following experimental data:
A decolorizes Br 2 in CCl4 and adds one eq. of H2 under mild conditions, forming B, C 9H10.
At high temperature and pressure, A adds four eq. of H 2. Vigorous oxidation of A yields phthalic acid, 1,
2C6H4(COOH) 2.

Page 20

Solution:
A has 6 of unsaturation, four of which often signal the presence of a benzene ring, as confirmed by isolation of
phthalic acid on vigorous oxidation. Reaction with Br 2 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 5 of unsaturation have been accounted
for the 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. T he structure is indene.
COOH
[O]

H2

3H2

COOH
Phthalic acid

Bicyclo[4.3.0] nonane

Indane, (B)

Indene, (A)

Example 4:
Identify (a) the chiral compound C, C 10H14, that is oxidized with alkaline KMnO 4 to PhCOOH and (b) the
achiral compound D, C10H14, inert to oxidation under the same conditions.

Solution:

(a) C is a monoalkyl substituted benzene with four Cs in the side chain. The only R with four Cs, one of which is
a chiral center, is CH(CH3)CH2CH3; C is secbutylbenzene, PhCH(CH3)CH2CH3. (b) Any R attached to the
benzene ring cannot have a benzylic H (no oxidation); D is tertbutylbenzene, PhCMe 3

Example 5:
(a) Give the structures for all possible chiral compounds, C 10H12, that do not decolorize Br 2 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 Br 2 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
monoRsubstituted fivemembered or diRsubstituted fourmembered ring. Only in this way can we
account for the additional four Cs of the formula.
H Me

1Methylindane

Me
H
H
Me
trans1, 2Dimethylbenzcyclobutane

Et
1Ethylbenzcyclobutane

(b) The extra unsaturation is in the single side chain. E is 3phenyl1butene, CH3CHCH=CH2.
Ph

EXERCISE I
AIEEE-SINGLE CHOICE CORRECT
1.

Oxidation of benzene with air at 723 K in the presence of V2O5 gives

(a) Malic acid
(b) Maleic acid
(c) Malonic acid
(d) Maleic anhydride

2.

nButyl benzene on oxidation will give

(a) Benzoic acid
(c) 4Phenyl butanoic acid

3.

(b) Butanoic acid

(d) Benzaldehyde

Which reaction sequence would be best to prepare 3chloroaniline from benzene?

(a) Chlorination, nitration, reduction.
(b) Nitration, chlorination, reduction.

Page 21

(c) Nitration, reduction, chlorination.

(d) Nitration, reduction, acylation, chlorination, hydrolysis.
4.

All the following groups are activating ortho, para directors when attached to a benzene ring except
O
(b) NHCCH3
(d) N(CH3)2

(a) OCH3
(c) Cl
5.

Rank the following compounds in terms of increasing reactivity towards nitration with conc. HNO 3/
conc. H2SO4.

(1)

Cl

NHCH3

(2)

(3)

(a) (1) < (2) < (3)

(c) (3) < (1) < (2)
6.

(b) (2) < (1) < (3)

(d) (3) < (2) < (1)

For the reaction,

Br
?
NO2
the best reactants are
(a) C6 H5Br + HNO3 , H2 SO4
(c) C6 H5NO2 + Br2, FeBr3
7.

(b) C6 H5Br + H2SO4,

(d) C6 H5NO2 + HBr

Consider the following statements concerning the effect of a trifluoroemethyl group, CF3 , on an
electrophilic aromatic substitution.
1. The CF3 group will activate the ring.
2. The CF3 group will deactivate the ring.
3. The CF3 group will be a meta director.
4. The CF3 group will be an ortho, para director.
Which of these statements are correct?
(a) 1,3
(b) 1,4
(c) 2,3
(d) 2,4

8.

Among the following, the compound that can be most readily sulphonated is
(a) benzene
(b) nitrobenzene
(c) toluene
(d) chlorobenzene

9.

Among the following statements on the nitration of aromatic compounds, the false one is
(a) The rate of nitration of benzene is almost the same as that of hexadeuterobenzene.
(b) The rate of nitration of toluene is greater than that of benzene.
(c) The rate of nitration of benzene is greater than that of hexadeuterobenzene.
(d) Nitration is an electrophilic substitution reaction.

10.

Which of the following reactions is not an example of electrophilic substitution

AlCl3
C6H5CH(CH3)2
(a) C 6H6 CH 2 CH CH 3
AlCl3
C6H5 CH 2 Cl
(b) C 6H6 CH 2 Cl 2
UV light
(c) C 6H6 3 Cl 2 C 6H6 Cl 6

Page 22

OH
AlCl

3
(d) C 6H5 OH CO HCl

CHO
11.

Which of the following is meta directing group?

(a) COOH
(b) OH
(c) NH2
(d) Cl

12.

In the nitration of benzene with a mixture of conc. HNO 3 and conc. H2SO4, the active species involved
is

13.

(a) NO 3

(b) NO2

(c) NO 2

(d) NO 2

In the sulphonation of benzene, the active species involved is

(a) HSO 4

(b) SO3

(c) SO2

(d) SO 24

14.

Benzene reacts with acetyl chloride in presence of anhydrous aluminium chloride to form
(a) acetophenone
(b) phenyl acetate
(c) chlorobenzene
(d) benzoic acid

15.

The direct iodination of benzene is not possible because

(a) I2 is an oxidising agent.
(b) resulting C6H5I is reduced to C6 H6 by HI
(c) HI is unstable
(d) the ring gets deactivated

16.

Identify the correct order of reactivity in electrophilic substitution reactions of the following compounds:
CH3

(I)

(II)

(a) (I) > (II) > (III) > (IV)

(c) (II) > (I) > (III) > (IV)

Cl

(III)

NO2

(IV)

(b) (IV) > (III) > (II) > (I)

(d) (II) > (III) > (I) > (IV)

17.

Sulphonation of benzene differs from most of the electrophilic aromatic substitution reactions. Which
one of the following statement is correct?
(a) is reversible.
(b) requires the presence of Lewis acid as catalyst.
(c) takes place with explosive violence.
(d) requires elevated temperature.

18.

Benzene reacts with npropyl chloride in the presence of anhydrous AlCl3 to give predominantly
(a) npropyl benzene
(b) isopropyl benzene
(c) 3propyl1chloro benzene
(d) no reaction

19.

Which one of the following will undergo meta substitution on mono chlorination?
(a) chloro benzene
(b) phenol
(c) ethyl benzoate
(d) ethoxy benzene

20.

NH2, Cl, OH and CH3 groups when attached to benzene ring activate/deactivate it for electrophilic
substitution reaction. Their decreasing order of activation is
(a) NH2 > OH > Cl > CH3
(b) NH2 < Cl > OH > CH3

Page 23

(c) NH2 > OH > CH3 > Cl

(d) OH > NH2 > Cl > CH3

21.

The function of anhydrous aluminium chloride in the Friedel-Crafts reaction is

(a) to absorb water.
(b) to absorb hydrochloric acid.
(c) to produce an electrophile.
(d) to produce nucleophile.

22.

Isopropylbenezene can be obtained by

23.

(a)

+ CH3CH=CH2

(c)

CH3

CHCl

H+

AlCl3

+ CH3 CH2CH2Cl

(b)

AlCl3

(d) all of these

CH3
A particular form of tribromobenzene (A) melts at 44C. On nitration it forms one possible mononitro
tribromo benzene. The structure of compound (A) is

Br

Br

Br
(a)

(b)

Br

Br
Br
Br
Br

(c)

(d) Both (a) and (b)

Br
24.

To prevent the formation of carbocation in Friedal craft alkylation the best possible condition
(a) AlCl3 + high temperature
(b) SnCl4 + high temperature
(c) AlCl3 + low temperature
(d) SnCl4 + low temperature
NO2

25.

To prepare
(a)
(b)
(c)
(d)

from

, which of the following is the correct sequence of steps?

Et
Nitration followed by Friedel Crafts ethylation.
Friedel Crafts ethylation followed by nitration.
Friedel Crafts acylation (CH3COCl), nitration followed by Clemensons reduction.
Friedel Crafts acylation (CH3COCl), Clemensons reduction followed by nitration.

EXERCISE II
IIT-JEE- SINGLE CHOICE CORRECT
1.

Chlorination of toluene in the presence of light and heat followed by treatment with aqueous NaOH
gives
(a) ocresol
(b) pcresol
(c) 2, 4dihydroxytoluene
(d) benzoic acid

2.

For the electrophilic substitution reaction involving nitration, which of the following sequence regarding
the rate of reaction is true?
(a) k C6H6 k C6D6 k C6T6
(b) k C6H6 k C6D6 k C6T6
(c) k C6H6 k C6D6 k C6T6

(d) k C6H6 k C6D6 k C6T6

Page 24

3.

Which of the following statement made on FriedelCrafts reaction is false?

(a) Friedel Crafts alkylation and acylation leads to new carboncarbon bond formation.
(b) Alcohol/acid combination can be used as reagent for FriedelCrafts alkylation.
(c) When
benzene
and
nitrobenzene,
both
liquids,
are
mixed
and
treated
with
CH3COCl/AlCl3 under proper reaction conditions, the products obtained are macetyl nitrobenzene
and acetophenone.
(d) npropylbenzene can be made in good yield from benzene using npropyl chloride and anhydrous
AlCl3 combination as reagent at low temperature.

4.

The presence of which one of the following groups on benzene nucleus activates it towards
electrophilic substitution?
(a) CN
(b) CHO
(c) COOR
(d) OCOR

5.

The halide that will not react with benzene in the presence of anhydrous AlCl 3 is
(a) CH3CHClCH3
(b) C6 H5CH2Cl
(c) C6 H5Cl
(d) CH3CH2CH2Cl

6.

Which of the following species is expected to have maximum enthalpy in an electrophilic aromatic
substitution reaction?

E+

+ E+
(II)

(IV)

(III)

(a) Species (II)

(c) Species (IV)

8.

E
+

(I)

7.

(V)

(b) Species (III)

(d) Species (V)

The relative reactivities of benzene, aniline, nitrobenzene and toluene are

(a) benzene > toluene > aniline > nitrobenzene
(b) nitrobenzene > aniline > toluene > benzene
(c) toluene > aniline > nitrobenzene > benzene
(d) aniline > toluene > benzene > nitrobenzene
During electrophilic substitution the major product in the following reaction will be

+ Cl2

FeCl3

N
H

Cl
(a)

N
H

(c)

Cl

(b)

N
H
(d) both (a) & (b)

N
Cl
9.

Electrophile NO 2 attacks the following aromatic species.

Page 25

CCl3

NO2

(I)

(II)

NH3

(III)

(IV)

In which cases NO 2 will be at meta position?

(a) (II) and (IV)
(b) (I), (II) and (III)
(c) (II) and (III) only
(d) (I) only
10.

Which one of the following aromatic compounds fails to undergo FriedelCrafts reactions?
(a) C6 H5CH3
(b) C6 D6
(c) C6 H5NO2
(d) C6 H5Cl

11.

Phenol reacts with bromine in carbon disulphide at low temperature to give

(a) mbromophenol
(b) o and pbromophenol
(c) pbromophenol
(d) 2,4,6tribromophenol

12.

Benzene on reaction with conc. HNO 3 in presence of conc. H2SO4 followed by the treatment of Cl2 in
presence of FeCl3, gives
(a) 2chloro1nitrobenzene
(b) 3chloro1nitrobenzene
(c) 4chloro1nitrobenzene
(d) a mixture of 2chloro and 4chloro1nitro benzene

13.

Which of the following substituted benzenes would furnish three isomeric compounds when one more
substituent is introduced?
Cl
Cl
Cl
Cl
Cl
(1)
(2)
(3)
(4)
Cl

Cl
Select the correct answer using the codes given below:
(a) (1), (2) and (3)
(b) only (1)
(c) (2) and (4)
(d) (1) and (3)
14.

Toluene when treated with Br2/Fe gives pbromotoluene as the major product because the CH3 group
(a) has I effect.
(b) is meta directing.
(c) activates the ring by hyperconjugation. (d) deactivates the ring.

15.

The major product formed on nitration of N, Ndimethylaniline with conc. H2SO4/HNO3 mixture is

NMe2

NMe2

NMe2
NO2

(a)

(b)

NMe2
NO2

(c)

(d)

NO2
NO2
16.

NO2

Which of the following reaction is wrong?

Page 26

CH3

(a)

+ CH3Cl

Anhydrous
AlCl3

CH2CH2CH3
+ CH3CH2CH2Cl

(b)

Anhydrous
AlCl3
Room
Temperature

CH(CH3)2
+ CH3CH2CH2Cl

(c)

Anhydrous
AlCl3
Room
Temperature

O
CH3C

(d)

17.

+ CH3COCl

Anhydrous
AlCl3
Room
Temperature

Which of the following triad of group activates the benzene ring and directs the electrophile to o and
pposition for substitution?
(a) NO2, CHO, COOH

(b) OH, O, CH3

(c) OH, SO2 OH, NO2

(d) NH2, CHO, SO2 OH

O
+ CH3CH2CCl

18.

Anhydrous
AlCl3

(X)

The structure of (X) would be

O
C
(a)

(b)

O
OH
(c)

(d)

CCl3
Cl2, Fe

19.

X. What is X as a main product?

CCl3

CCl3
Cl

(a)

(b)

Cl

Page 27

CCl3

CCl3

Cl

Cl
(c)

(d)

Cl

Cl
20.

pNitrotoluene on further nitration gives

CH3

CH3
NO2

(a)

(b)

NO2
NO2

NO2

CH3

CH3
NO2

(c)

21.

22.

(d)

NO2
O2N
NO2
Which of the following statements is correct?
(a) Bromination of toluene occurs faster than that of benzene.
(b) Nitration of toluene is difficult than that of nitrobenzene.
(c) The bromonium ion is a good nucleophile.
(d) Effective nitrating agent is nitrate ion.
The order of reactivity of following compounds

CH3

CH2CH3

CH2(CH3)2

(I)

(II)

(III)

C(CH3)3

(IV)

towards electrophilic substitution will be-[where = C6H5 ]

(a) (I) > (II) > (III) > (IV)
(c) (II) > (I) > (III) > (IV)
23.

(b) (IV) > (III) > (II) > (I)

(d) (III) > (II) > (I) > (IV)
NO2+BF4

CH2

(X). What is the product (X) formed in the reaction.

O2N
NO2

NO2
(a)

(b)

CH2

CH2
O 2N

O2N
(c)

CH2

NO2

(d) both (b) and (c)

O2N
COCl

24.

Anhydrous
AlCl3

(X). The major product

COCl

H
C=O
(a)

C=O

(b)

Page 28

(c)

(d) all of these

O
C

Br2/Fe(1eq)

25.

Br

O
Br

(a)

(b)

Br

C
Br

(c)

N +

(d)

EXERCISE III
MORE THAN ONE CHOICE CORRECT
1.

Which of the following groups is/are deactivating but o/pdirecting?

(a) Cl
(b) CH2Cl
(c) NO2

2.

(d) NO

Which of the following compound will direct the incoming electrophile to the meta position?

CF3

OCH3
(a)

(b)

CHO

CH2OH

(a)
3.

(d)

In the given sequence of reaction,

+ methyl succinic anhydride

Anhydrous
AlCl3

Me

CH2
CO2H

Zn / Hg
Conc. HCl

(B)

SOCl2

(C)

AlCl3

(D)

CH CH
2
(a) (A) is

(A)

(b) (A) is

CH2
CHCH3
CO2H

Page 29

Me
(c) (D) is

(d) (D) is

Me
O

O
4.

Which of the following is not a suitable method to prepare, PhCH2 CH2 Ph?
Anhydrous

(a) 2PhH + CH2Cl2

AlCl3

Anhydrous

(b) PhH + ClCH2CH2Ph

AlCl3 , low temp.

(c) PhH + CH3CHPh

Anhydrous
AlCl3

Cl
(d) PhH + PhCH2CCl

O
5.

Anhydrous

Zn / Hg

AlCl3

Conc. HCl

A chiral compound (A) with molecular formula C 10H12 do not decolourize Br2 water but can be oxidised
to phthalic acid. The possible structure of (A) could be
H Me
(a)

Me

(b)
Me
H
Me
H

(c)

H
Me
H
H
Me

(d)

SMe2
6.

What is the correct about the given compound,

(a)
(b)
(c)
(d)

7.

The
The
The
The

compound is more reactive than benzene towards electrophilic substitution.

compound is less reactive than benzene towards electrophilic substitution.
inc oming electrophile will be directed towards orthopara position.
incoming electrophile will be directed towards meta position.

Which of the following compounds are meta directors?

CH2Cl

CCl3

(a)

(b)

CH2NMe3

NMe3
(c)

8.

(d)

+ CH3CH=CH2
+ CH2=CHCH2Cl

HF, 0C

Anhydrous
ZnCl2

(A)
(B)

Which is the correct about (A) and (B)?

Page 30

CH
(a) (A):

CH3

CH2CH=CH2

CH3

(b) (B):

CH2CH=CH2

CH

(c) (A):
9.

(d) (B):

CH3

The groups that are activating and orthopara directing would be

O
O
(a) OCCH3

(b) SCH3

(d) SCH2Cl

(c) CH2CH2NMe3
10.

CH3

Which of the following combination of reagents or sequence of reactions can give linear alkyl benzene
(LAB)?
(a)

+ CH3CH2CH2Cl

Anhydrous

(b)

+ CH3CH2CH2Cl

FeCl3

(c)

+ CH3CCH2Cl

AlCl3,

?
?

Anhydrous

Zn / Hg

AlCl3

Conc. HCl

O
(d)

+ CH3CH2CCl

Anhydrous

Zn / Hg

AlCl3

Conc. HCl

EXERCISE IV
MATCH THE FOLLOWING
1.

Compare the
as standard.

rates

of

bromination

of

given

Column I
Compounds

compounds,

relative

to

benzene

taken

Column II
Rate of Bromination

I.

C6H5OCH3

(A) 1012

II.

C6H5N(CH3 )2

(B) 10

III. C6H5CH3

(C) 105

IV. C6H5NO2

(D) 1
(E) 109

2.

Page 31

Column I
Groups attached to benzene

Column II
Effect of the group

I.

N(CH 3 ) 3

(A) I, +R

II.

CH=CH2

(B) I, R

III. OCH3

(C) I only

IV. NO2

(D) +I, +R
(E) I, +R, R

3.
Column I
Groups attached to benzene

Column II
Nature of the group

I.

OH

(A) strongly deactivating, ortho para directing

II.

Br

(B) strongly activating, ortho-para directing

III. NO2

(C) weakly deactivating, ortho-para directing

IV. NHCOCH3

(D) strongly deactivating, meta directing

(E) Moderately activating, ortho-para directing
ASSERTION AND REASON

Direction: Read the following questions and choose

(A)
(B)
(C)
(D)
1.

If both Assertion and Reason are true and Reason is the correct explanation of the assertion
If both Assertion and Reason are true but Reason is not correct explanation of the Assertion.
If Assertion is true but Reason is false.
If Assertion is false but Reason is true.

Assertion: methyl nitrobenzene should be prepared by the nitration of benzene followed by its
ethylation of nitrobenzene.
Reason: nitro group is meta directing group.
(a) (A)
(b) (B)

2.

(c) (C)

(d) (D)

Assertion: Alkylation of benzene by Friedel-Crafts reaction gives polyalkylated benzene.

Reason: The ring gets activated for further substitution after the introduction of one alkyl group.
(a) (A)
(b) (B)
(c) (C)
(d) (D)

3.

Assertion: Nitration of aniline can be done by protecting NH2 group by acetylation.

Reason: Aniline ring is oxidized by concentrated HNO 3.
(a) (A)
(b) (B)
(c) (C)

4.

(d) (D)

Assertion: In strongly acidic solution, aniline becomes more reactive toward electrophilic reagents.
Reason: The amino group is completely protonated in strongly acidic medium. The lone pair of electrons
on the nitrogen, therefore, is no longer available for resonance.
(a) (A)
(b) (B)
(c) (C)
(d) (D)

5.

Assertion: A mixture of concentrated nitric acid and concentrated sulphuric acid is better than
concentrated nitric acid for electrophilic nitration of benzene.

Reason: H2 SO4 is a stronger acid than HNO 3 which accelerates formation of N O 2 electrophile.
(a) (A)
(b) (B)
(c) (C)
(d) (D)

Page 32

PASSAGE BASED PROBLEMS

Electrophilic substitutions are characteristic reactions of aromatic compounds. In this reaction hydrogen
of the aromatic ring is easily replaced by an electrophile because hydrogen in the form of H+ is a very good
leaving electrophile. CO 2 and SO3 are also good leaving electrophiles when COOH and SO3H groups are
present either at ortho or at para position to the highly activating groups like NH2 and OH etc. Electrophilic
substitution reactions become difficult in presence of electron withdrawing groups. Position of incoming
electrophile depends on several factors like electronic and steric effect of already present group,
intramolecular hydrogen bonding and the temperature at which reaction is being done. All electron donating
groups also activate oxidation of aromatic compound beside activating electrophilic aromatic substitution.

OH
SO3H

aq.)
Br
2 (
(X)

1.

excess

The compound (X) is

OH
Br

OH
SO3H

(a)

Br

SO3H
(b)

Br
2.

OH

Br

(c)

(d)

Br

Br

Which of the following compound will not give electrophilic aromatic substitution?

CH3

NO2

(a)

(b)

CH3

H3C

OH

O2N

NO2

NO2
(c)

(d)

O2N

OH
3.

OH
Br

NO2

2, 4, 6Trinitrophenol (picric acid) can be prepared by treating phenol with cold concentrated H2 SO4
followed by treatment with hot concentrated HNO 3 . In this process:
(a) Cold concentrated H2SO4 makes sulphonation at ortho position which accelerates oxidation of
aromatic ring by concentrated HNO 3.
(b) SO3H group incorporated at ortho position is also substituted by NO2 group on treatment with
HNO3.
(c) SO3H group at ortho position further activates the ring towards electrophilic substitution.
(d) all the above statements are false.

4.

What is the correct order of rate of electrophilic aromatic substitution among following compounds?

CH3

CH3

CH3
CH3

(1)

(2)

(a) (2) > (3) > (1) > (4)

(3)

CH3

(4)

(b) (1) > (2) > (3) > (4)

Page 33

(c) (3) > (2) > (1) > (4)

(d) (2) > (1) > (3) > (4)

EXERCISE V
SUBJECTIVE PROBLEMS
1.

Using resonance contributors, answer the following. Which is a more stable carbocation intermediate?

OH

CH3
or
+

NO2

2.

NO2

Give the products of the following reactions.

O

OCCH3
+ HNO3

(a)

H2SO4

CH3
1. Mg/Et2O
2. D2O

(b)

Br

OCH3
(c)

O
+

AlCl3

(d)

+ Br2

Fe

O
CH3
(e)

3.

CF3
1. NBS/
2. Mg/Et2O
3. ethylene oxide
4. H+

(f)

+ Cl2

FeCl3

Give the product(s) obtained from the reaction of each of the following compounds with Br 2 /FeCl3.

O
(a)

(b)

OC

(c) H3C

COCH3

CH2O

NO2
(d)

CH3O
4.

What products would be obtained from the reaction of the following compounds with hot and acidified
KMnO4?

CH2CH3
(a)

CH3
(b)

CH2CH2CH2CH3
(c)

CH3

CHCH3
C(CH3)3

5.

CH3

Propose a mechanism for each of the following reactions.

Page 34

CH2CH2CHCH=CH2
CH3

(a)

H3C

CH=CH2

CH3
+

(b)

6.

CH2CH3

Show how the following compounds could be prepared from benzene.

CH3

CH3C

(a)

OCH3
Br

SO3H

(b)

(c)

CH2CH(CH3)2
NO2

CH3C=CH2
7.

Determine the major product for each of the following reactions.

OH
CO2H
Br2 in
H2O

(a)

(b)

(c)

CH3
O

?
Anhydrous
AlCl3

Cl2/Fe

N
H

OEt
(d)

Conc. HNO3

CH2O
HCl
ZnCl2

8.

Compare the rate of nitration under similar conditions of PhOMe and PhSMe. Explain.

9.

PhNH2 reacts with Br2 in H2O to give more than 90% yield of 2,4,6tribromoaniline, while PhNMe2 is
mononitrated at the meta position with the more powerfully electrophilic reagent HNO 3/H2SO4. Explain.

10.

Explain the following percentages of meta electrophilic substitutions:

(a) ArCH3, ArCH2Cl, ArCHCl2 , ArCCl3
4.4%
15.5% 33.8% 64.6%
(b) ArN+Me3,
100%

ArCH2N+Me3 ,
88%

ArCH2CH2N+Me3
19%

Page 35

ANSWERS
EXERCISE I
AIEEE-SINGLE CHOICE CORRECT

1. (d)

2. (a)

3. (b)

4. (c)

5. (d)

6. (a)

7. (c)

8. (c)

9. (c)

10. (c)

11. (a)

12. (d)

13. (b)

14. (a)

15. (b)

16. (c)

17. (a)

18. (b)

19. (c)

20. (c)

21. (c)

22. (d)

23. (a)

24. (d)

25. (c)

EXERCISE II
IIT-JEE SINGLE CHOICE CORRECT

1. (d)

2. (c)

3. (c)

4. (d)

5. (c)

6. (a)

7. (d)

8. (d)

9. (b)

10. (c)

11. (b)

12. (b)

13. (d)

14. (c)

15. (a)

16. (b)

17. (b)

18. (a)

19. (b)

20. (a)

21. (a)

22. (a)

23. (d)

24. (c)

25. (c)

EXERCISE III
MORE THAN ONE CHOICE CORRECT

1. (a, d)

2. (b, c)

3. (b, d)

4. (a, c)

6. (b, d)

7. (b, c, d)

8. (a, b)

9. (a, c, d)

5. (a, d)
10. (b,c,d)

EXERCISE IV
MATCH THE FOLLOWING
1.

I (E) ; II (A) ; III (B) ; IV (C)

2.

I (C) ; II (E) ; III (A) ; IV (B)

3.

I (B) ; II (C) ; III (D) ; IV (E)

Page 36

ASSERTION AND REASON

1. (d)

2. (a)

3. (a)

4. (d)

5.

(a)

PASSAGE BASED PROBLEMS

1. (c)

2. (d)

3. (b)

4. (c)

EXERCISE V
SUBJECTIVE PROBLEMS

OH
1.

is the most stable Intermediate.

NO2

OH

OH

OH

OH

2.

etc

H NO2
H NO2
H NO2
H NO2
Here OH stabilises adjacent carbocation by +R effect but in the other one methyl stabilizes the adjacent
carbocation only by +I effect.
OCOCH3
OCOCH3
CH3
CH3
NO2
(1) Mg/Et2O
+
(a)
(b)
(2) D2O
Br
D
NO2
(Major)

(Minor)

OCH3
CO(CH2)2COOH

OCH3
(c)

C=O
CH2CH2COOH

N
(d)

Br
+

(Minor)

Br

(Minor)

(Major)

(Major)

CH2CH2CH2OH

CF3

(e)

(f)

Cl
3.

(a)

(c)

O
O C

Br

O
C

CH3

(b)

O
COCH3

(a)

NO2
(d)

Br

COOH
(b)

COOH

Br

OCH3

Br
COOH
4.

CH2 O

COOH
(c)

COOH

C(CH3)3

Page 37

CH3

CH3
(CH2)2CHCH=CH2

(CH2)2CHCH CH3

5.

(a)

CH3
(CH2)2CCH2CH3

1, 2 hydride shift

CHCH3
H

(b)

CH=CH2

CH3

CH3

H
CH3

CH3Cl,

(a)

CHCH3

CH3

CH3

CH3
CH3CH=CH2

alc KOH,

1 eqv. Cl2 + h

Heat

AlCl3,

H3C
CCl
H3C

H3C
CH
H3C

Heat

(4)

COCH3

COCH3
(CH3)2CHCH2Cl + AlCl3

(b)

AlCl3 +

CH2CHMe2
NO2
Conc. HNO3

(c)

Conc. H2SO4

CH3COCl,

Cold
(No rearrangement)

CH2CH(CH3)2

SO3H
CH2CH(CH3)2

NO2

NO2

NO2
Br2/Fe

NaOCH3,

Br2/Fe

+ conc.H2SO4

Br

Br
Br

OH

OH

Br

Br
7.

(a)

(b)

OEt
(d)

9.

Cl
(c)

Br
OCH3

CH3
O
N
H

Br

8.

CH=CH2

6.

OEt
Cl

NO2
NO2
PhOMe > PhSMe. The bond from O (which uses a 2porbital) to the ring C is shorter and stronger
than the comparable bond from S (which uses a 3porbital) to the ring C.
The tribromoderivative forms because NH2 is a strongly activating o,porienting substituent (as is
NMe2). Recall that amines are also proton acceptors, so in strong acid they are completely protonated.

Page 38

10.

Consequently, the only species present in HNO 3/H2SO4, is the conjugate acid PhNMe2H+ and it is the
species undergoing nitration. The NR 2H+ group, with a full + charge, is a deactivator that orients meta.
(a) Successive replacement of Hs in electronreleasing CH3 by electronegative Cls makes G
increasingly electronattracting and morienting.
(b) The + charge on N in +NMe3 makes the substituent electronattracting and mdirecting by an
inductive effect. Its influence wanes with increasing CH2s between +N and Ar. With two CH2s, the
electronreleasing effect of the alkyl group is more significant and o,porientation dominates.

MIND MAP
NR3, NO2, CN, SO3H,
CHO, COR, CO2H, CO2R,
+

O , NH2, NHR, NR2, OH,

OR, NHCOR, R, Ar, COO

F,Cl, Br, I

CONH2,

Activating

Deactivating

o, p directing groups

1. PhH + RX

mdirecting groups

PhR.
Directing groups

2. PhH + RCOX

PhCOR

Carbocation can also be formed from

ROH, Alkene or CO in presence of
acid to give electrophilic substituted
product.
Alkylation may involve rearrangement.
With phenol excess AlCl3 and with
aniline excess AlCl3 is required for
alkylation. In case of aniline
unexpected meta alkylated product is
obtained.

Friedel Crafts
reaction

ELECTROPHILIC
AROMATIC
SUBSTITUTION
Halogenation

PhH + conc. H2SO4

PhSO3H

Deprotonation is rate determining step.

Nitration

Sulphonation

PhH + X2

PhX.

PhH + conc. HNO3 + H2SO4

PhNO2

Electrophilic attack to benzene ring is

rate determing step. Other nitrating
species are N2O5, NO2+ BF 4 and
NO2+ ClO4.

Page 39