ELECTROPHILIC SUBSTITUTION REACTION:
This type of substitution reaction is initiated by the formation of electrophiles as a
substituents or attacking reagent. Electrophiles are either positively charged species or neutral
species with electro deficiencies. Most electrophilic substitution reaction takes place in aromatic
systems due to presence of pi electron (high negative charge density). For our convenience we
are considering benzene as our substrate.
Directive influence of substituent in Electrophilic Substitution Reaction:
In electrophilic substitution atoms or group of atoms already attached to the aromatic
ring influences the position of electrophilic substitution to either ortho and para position or only
to meta position. This is called directive influence or orientation effect.
Ortho & para directive: Electron donating groups or atoms can orient the incoming electrophile
to ortho and para positions.
Example: -NH2 > -OH > -OR > -NHCOR > -OCOR > -C6H5 > -CH3 > -X
Meta directive: Electron withdrawing groups can orient the incoming electrophiles to get
attached to meta position.
Example: -NO2 > -CN > -SO3H > -CHO > -COOH > -COOR > -CONH2
This is to be mentioned that o- and p- directing groups increase electron density on the benzene
ring facilitating electrophilic substitution reaction. Such groups are ring activating groups. On the
contrary, m- directive groups reduce electron density on the aromatic ring and therefore
decreases the rate of electrophilic substitution. Such groups are ring deactivating groups.
Nitration of Benzene:
When benzene is heated with the mixture of conc. HNO3 and conc. H2SO4 which is
known as mixed acid at about 600 C give nitrobenzene. This mixed acid rapidly generates
highly reactive nitronium cation (NO 2+) which acts as an electrophile in this reaction.
Mechanism of nitration of benzene
This reaction involves the following steps:
Halogenation of Benzene:
Benzene reacts with halogen in presence of a Lewis acid such as FeCl 3 to give halobenzene.
For example, chlorine reacts with benzene in presence of ferric chloride or AlCl 3 as catalyst to
give chlorobenzene.
Similarly, benzene reacts with bromine in presence of ferric bromide as catalyst to give
bromobenzene.
Mechanism of chlorination of benzene
This reaction involves the following steps:
Friedel – Craft’s reaction of benzene:
Friedel- Craft’s reaction is of two types- alkylation and acylation. Alkylation is done by treating
benzene with an alkyl halide in presence of Lewis acid. Acylation is carried out by treating
benzene with an acid halide in presence of Lewis acid.
Friedel Craft’s alkylation reaction
A electrophile involved in this reaction is a carbocation which is produced by the reaction
between Lewis acid AlCl3 and 2 and 3 alkyl halide. 1 alkyl halide is not considered as a
reactant as it does not produce the required carbocation while reacting with Lewis acid AlCl 3.
Mechanism of Friedel-Craft’s alkylation reaction:
This reaction involves the following steps:
Friedel craft’s acylation reaction:
Introduction of an acyl group in the benzene ring by treating benzene with an acylating
agent like acid chloride (RCOCl) or acid anhydride in the presence of anhydrous AlCl 3 is known
as Friedel- Craft’s acylation reaction. Eg.
Mechanism of Friedel-Craft’s acylation reaction:
This reaction involves the following steps:
