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X X X X
ELECTROPHILIC AROMATIC SUBSITUTION Y

IN MONOSUBSTITUTED BENZENE
Y

➢ Since all the six hydrogen atoms of benzene nucleus Benzene Monosubstituted derivative
ortho- meta-
Y
para-
are identical; when one group (say X) is introduced Disubstituted derivative
into the benzene nucleus, only one product is ➢ However, experiments have shown that all the three
obtained. products are never formed to quantitative yield and
➢ On the other hand, when a second substituent (say Y) actually the main product is either a mixture of ortho
is induced in a monosubstituted derivative, three and para-isomers (m-isomer being negligible in amount)
isomeric disubstituted products are possible. or only the meta-isomer (o-, and p- isomers being
negligible in amounts).

ur
nn
➢ Further experiments have shown that it is the nature of
the group already present (X in above case) on the
benzene nucleus that directs the new incoming group (Y
ka
mc
in above case) either to ortho and para positions (both)
or only to meta position.
➢ This effect of the group already present on the nucleus is
sg

known as directive influence of the group or orientation

effect.
➢ Substituents either activate or deactivate a benzene ring
➢ On the basis of this effect the known groups in organic
towards electrophile, and direct selective substituents at
chemistry have been classified into two types.
cp

specific site on the ring.

s@
tk

➢ On the basis of above two effect the known groups in
organic chemistry have been classified into three types.
➢ Type 1. Ortho, para director and activators: Substituents
that activate a benzene ring and direct substitution at
ortho and para positions.
➢ Type 2. Ortho, para director and deactivators:
Substituents that deactivate a benzene ring and direct
substitution at ortho and para positions.

➢ Type 3. Meta director (Deactivators): Substituents that

direct substitution at meta positions. All meta directors
deactivate the ring.

1

➢ The electronic density in the benzene nucleus is
generally effected by one or the other of the following
effects.
(i) Inductive (I).
mc
(ii)Electromeric (E).
(iii) Mesomeric (M).
(iv) Hyperconjugation.
sg
➢ Now if the group (already present) pushes the electrons
away from itself and to the benzene ring it is given plus
sign (viz. +I, +E, and +M).
cp
s@
tk
➢ Since such groups take electrons from the o- and p-
positions, i.e., they decrease the electrons density in
these positions, they cause the new entering
electrophilic group to go the m-position which is
having relatively high electrons density.
➢ Moreover, since the m-position is almost unaffected
and the o and p-positions have decreased electron
density, the group is said to deactivate the benzene
nucleus, i.e., it hinders the further substitution and
hence, known as deactivating group.
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Orienting Influence on the Basis of Electronic Theory
➢ The orienting (directive) influence of groups can be
explained on the basis of electronic theory.
➢ In benzene the substitution is mainly electrophilic and
therefore, the electrophilic reagent will attack at that
position of the ring where electron density is maximum
and hence, any group or substituent that increases the
electron density in the benzene ring will facilitate
further substitution. i.e., causes the benzene ring to be
more reactive than benzene itself and vice-versa.
ur
nn
➢ Such groups increase the electrons density of the
ka
benzene nucleus in the o- and p-positions and thus, they
direct the new entrant to the o- and p-positions,
moreover since such groups increase the electrons
density in the nucleus, they facilitate the further
electrophilic substitution and hence, known as
activating groups.
➢ On the other hand, if a group pulls the electron from
the benzene nucleus towards itself, they are assigned
minus sign (viz. -I, -E, and -M).
X Y
+I Effect -I Effect
The arrow shows the direction of the electrons movement
➢ In general, all the o, p-directing groups, except
halogens, activate the ring towards electrophilic
substitution and hence, known as activating groups;
while the m-directing groups deactivate the ring
towards electrophilic substitution and hence, knows
as deactivating groups.
2

➢ If the two or more effects proceed in the opposite
directions, i.e., one is positive and other is negative then
the substitution will be governed by the more powerful
effect. Now we will give some important examples of o-
, p- and m -directing groups.
o & p -DIRECTING GROUPS
➢ Note that all o-,p-directing groups, except alkyl, have
unshared pair of electrons on the atom attached to the
benzene nucleus (key atom), e.g.,
mc
➢ Note that in the above formulae the electromeric
sg
effect increases the electron density in the o- and p-
positions and hence, the electrophilic species will
attack both the o- and p-positions but not the meta.
cp
s@
tk
➢ Thus, the electron density in the o- and p-positions is
further increased by the mesomeric effect and hence,
the compound will undergo substitution in the o- and
p-positions.
➢ It must be remembered that the mesomeric effect is a
permanent effect whereas the electromeric effect is a
temporary one but they never oppose each other.
➢ The sum total of both the effects is known as
tautomeric (T) or conjugative effect.
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1. Effect of Hydroxyl Group: The unshared pair of
electrons on the key atom of the group causes the
compound to undergo electromeric and mesomeric
effects.
➢ Electromeric effect (E). One of the unshared pair of
electrons can undergo electromeric shift by interacting
with π-electrons of the ring as shown below.
ur
nn
➢ Mesomeric effect (M). The presence of a lone pair of
ka
electrons is further responsible for another important
effect by increasing the number of resonating structures
of the compound. Such effect is known as mesomeric
(M) or resonance effect.
➢ Inductive effect (I): on the other hand, it should be noted
that the -OH group also induces the minus inductive
effect (- I) which will oppose the o, p-substitution and
favor the m-substitution, but as the +T effect is more
powerful than the -I effect, the substitution will be
facilitated and taking place in the o-, p- positions.
3

➢ Thus, the activation and deactivation of the ring caused
by the substituent already present is brought about by
inductive, electromeric and mesomeric (resonance)
effects.
2. Effect alkyl groups: The alkyl group in the alkyl-
benzene is particularly interesting, since the group does
not have any lone pair of electrons, it will neither
undergo electromeric nor mesomeric (except Kekule's
structures for benzene) effects.
mc
sg
cp
s@
tk
➢ Thus, the o, p-directing influence of methyl group is
due to inductive and hyperconjugation effects.
➢ Formation of a lesser amount of ortho-product in case
of t-butyl group may partly be explained on the basis
of steric hinderance.
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➢ However, the alkyl group, e.g., methyl undergoes the
strong +I effect which increases the electron density in
the o, p-positions and hence, directs the entering group
in these positions.
➢ The importance of the inductive effect in directing the
further substitution in toluene can be judged by the
following observation; as the hydrogen atoms of the
methyl group are replaced by the halogens, which
exert -I effect, % of m-product increases at the expense
of the o, p-products.
ur
nn
ka
➢ The orienting influence of the alkyl group should,
therefore, be entirely due to inductive effect (but it is
not so, see later) which is in the following order:
CH3 < CH2CH3 < CH(CH3)2, < C(CH3)3
➢ It means that the activating effect (orienting effect) of
an alkyl group should also be in the same older, but in a
number of cases the order is found to be reverse.
➢ It is explained on the basis of hyperconjugation effect
which is greatest in the methyl group and lowest in ter-
butyl group.