Effect of substituents on reactivity of Benzene

There are two types of substituents that maybe present on benzene ring. These substituents maybe
electron-donating OR electron-withdrawing. The formers donate electron density towards the ring
and destabilize it and the later withdraw electrons from the ring.

Ortho-para and meta directing groups:

If a benzene is required to attach another substituent ,then the position of incoming electrophile is
determined by the group already present on the ring. These groups maybe ortho-para directing OR
meta-directing. Electrons donating groups donate electrons to the ortho and para positions and the
incoming electrophile is attached at these positions, while the electron withdrawing groups
withdraw electrons from ortho and para position and incoming electrophile is directed towards the
meta position rich in electrons. The ortho, para and meta positions in benzene ring are shown
below:

group
ortho ortho

meta meta
para

Now we will discuss some examples of ortho-para and meta directing groups along with their
resonance structures.

i. -SO3H sulfonic acid group is an electron withdrawing group, so it will direct the coming
electrophile towards the meta position.

The resonance structures of benzene sulfonic acid are as following:

O O O O O
  
O S OH O S OH O S OH O S OH O S OH
 

As we can see ortho and para positions are electron deficient and meta position has electronic cloud,
so the incoming electrophile can go to any of meta position as follows:

SO3H SO3H SO3H

+ E +
E E

ii. -COOH carboxylic acid group is also an electron withdrawing group, so it will also direct
the coming electrophile towards the meta position.

The resonance structures for benzoic acid are as follows:

 O O O O O
C OH C OH C OH C OH C OH
 

As we can see ortho and para positions are electron deficient and meta position has electronic cloud,
so the incoming electrophile can go to any of meta position as follows:

COOH COOH
COOH

E +
E E

iii. -NH2 amino group is an electron donating group and it will donate electrons towards
ortho and para positions hence favorably undergoing ortho para substitution.

The resonance structures of amino benzene are as follows:


 
NH2 NH2 NH2
NH2 NH2



As we can see ortho and para positions are electron rich, so the incoming electrophile can go to any
of ortho OR para position as follows:

NH2 NH2 NH2

NH2 E E
E + +

iv. -OH hydroxyl group is an electron donating group and it will give electrons towards
ortho and para positions.

The resonance structures are as follows:

 

O H O H O H OH
O H
 

As we can see ortho and para positions are electron rich, so the incoming electrophile can go to any
of ortho OR para position as follows:
 OH OH
OH E
+
E

v. -COOR ester group is an electron withdrawing group, so it will also direct the coming
electrophile towards the meta position.

The resonance structures are as follows:

O O O O
 O
C OR C OR C OR C OR C OR

 

As we can see ortho and para positions are electron deficient and meta position has electronic cloud,
so the incoming electrophile can go to any of meta position as follows:

COOR
COOR

E
E

vi. -NO2 nitro group is an electron withdrawing group, so it will also direct the coming
electrophile towards the meta position.

The resonance structures are as following:

  
O
O O O O
N O
N O N O N O N O
 

As we can see ortho and para positions are electron deficient and meta position has electronic cloud,
so the incoming electrophile can go to any of meta position as follows:

NO2 NO2

E
E

vii. -I iodo-group is an electron donating group and it will give electrons towards ortho and
para positions.

The resonance structures are as following:

  

I I I
I I



As we can see ortho and para positions are electron rich, so the incoming electrophile can go to any
of ortho OR para position as follows:

I
I E

E

E
viii. -F group is an electron donating group and it will give its lone pair of electrons towards
ortho and para positions.

The resonance structures are as follows:

  
F
F F F
F
 

As we can see ortho and para positions are electron rich, so the incoming electrophile can go to any
of ortho OR para position as follows:

F F
E

E