Monosubstituted derivatives of

Benzene

Dr.Gajanan Kalyankar
Associate Professor
Maliba Pharmacy College
Substitution in Monosubstituted
benzenes

S Sunstituent

-H
+S
benzene Monosubstitution Product
 Nature of influence exercised by substituent on
benzene ring

◦ Directive or Orientation Effect: The first

substituent (S)may direct the next incoming
substituent (E) to ortho, meta or para position,
depending on the nature of the first substituent.
This is called the directive or the Orientation
Effect.

◦ Activity Effect: The substituent already present may

activate or deactivate the benzene ring toward
further substitution. These effects are called the
activity effects.
 S S

E E

S Ortho
S
1
6 2
-H
5 3 +E
4 E
Meta

6
2
5 E
3
Para
 Directive or Orientation Effect
◦ Ortho-para Directing effect: Certain substituents
direct the second substituent to the ortho and
para positions simultanously. These are called
ortho-para directors.
◦ Examples: OH, NH2 CH3 , OCH3, NHCOCH3

O H

O H O H O H

N O 2

H N O 3

H 2S O 4
N O N O 2
2
phenol 2 -n itro p h e n o l 4 -n itro p h e n o l 3 -n itro p h e n o l
53% 47% 0%
Directive or Orientation Effect
 Meta Directing effect: Certain substituents
direct the second substituent to the meta
position. These are called meta directors.

NO2

NO2 NO2 NO2

NO2

HNO3

H2SO4
NO2 NO2
1-nitrobenzene 1,2-dinitrobenzene 1,4-dinitrobenzene 1,3-dinitrobenzene
5% 1% 94%
 Effect of substituent on Reactivity
 Activating substituent Or Ring activator
 A substituent which activates the aromatic
ring to further substitution, is called an Ring
activator
 Deactivating substituent Or Ring Deactivator
 A substituent which deactivates the aromatic
ring to further substitution, is called an Ring
deactivator
Effect of substituent on Reactivity

A c tiv a tin g G ro u p D e a c tiv a tin g G ro u p

NH2 NO2
 Classification of directing groups
Ortho Para Directors
Strongly Activating NH2 , NHR, NR2 , OH, OR

Moderately Activating NHCOR, NHCOAr, OCOR,

OCOAr
Weakly Activating R, Phenyl
Weakly Deactivating F, Cl, Br, I
Meta Directors
Moderately Deactivating CHO, COR,COOH,COOR,
CONH2,SO3H, CN
Strongly Deactivating NO2, NH3+, CCl3, CCF3
Effect of substituent on Reactivity
 Ortho para directors activates a ring
toward electrophilic substitution, where
as meta directing groups deactivates a
ring toward electrophilic substitution.
 Although –F,Cl, Br, and I are ortho, para
directors, these substituents deactivate an
aromatic ring in electrophilic substitution
.
Theory of Directive Effects

C H 3 C H 3
C H 3

P a ra A tta c k

H E H E
H E
III
I II

E s p e c ia lly s ta b le
Theory of Directive Effects

C H 3 C H 3
C H 3

H
H H M e ta A tta c k

E E
E
V I
IV V
Theory of Directive Effects

C H 3 C H 3
C H 3
H
H
H

E E O rth o A tta c k
E

IX
V III
V II
E s p e c ia lly s ta b le
Theory of Directive Effects

N O N O 2 N O 2
2

P a ra A tta c k

H E H E
H E
III
I II

E s p e c ia lly u n s ta b le
Theory of Directive Effects

N O N O 2
N O 2
2

H
H H M e ta A tta c k

E E
E
V I
IV V
Theory of Directive Effects

N O 2
N O 2 N O 2
H
H
H

E E O rth o A tta c k
E

IX
V II V III
E s p e c ia lly u n s ta b le
Theory of Directive Effects

N H N H 2 N H 2
2 N H 2

H E H E H E
H E
III IV
I II

Especially stable
Theory of Directive Effects

N H N H 2 N H
2 2

E E E

H H H
V I V II
V
Theory of Directive Effects

N H 2
N H N H N H 2
2 2
E
E E E

H
H H H

X X I
IX
V III

Especially stable
Theory of Directive Effects

O H O H O H
O H

H E H E H E
H E
III IV
I II

Especially stable
Theory of Directive Effects

O H O H
O H

E E
E

H H
H V I V II
V
Theory of Directive Effects

O H
O H O H O H
E
E E E

H
H H H

X X I
IX
V III

Especially stable
Theory of Directive Effects

C l C l C l
C l

H E H E H E
H E
III IV
I II

Especially unstable
Theory of Directive Effects

C l C l
C l

E E
E

H H
H V I V II
V
Theory of Directive Effects

C l C l C l
C l
E
E E E

H
H H H

X X I
V III IX

Especially unstable
Theory of Directive Effects
 Orientation of disubstitiuted products

OCH3 OCH3 OCH3

CH3

CH3

CH3
Theory of Directive Effects
 Orientation of disubstitiuted products

CH3 CH3 CH3

NO2

NO2

NO2
How will you convert ?

 Toluene to 4-Nitrobenzoic acid

 Toluene to 3-Nitrobenzoic acid
 CH 3 COOH

K 2 Cr 2 O 7
HNO 3 H 2 SO 4
H 2 SO 4
CH 3
NO 2 NO 2
1-methyl-4-nitrobenzene 4-nitrobenzoic acid

COOH COOH
toluene
K 2 Cr2 O 7
H 2 SO 4 HNO 3
H 2 SO 4

NO 2
benzoic acid 3-nitrobenzoic acid