COVENANT UNIVERSITY

FACULTY OF SCIENCE AND TECHNOLOGY

DEPARTMENT OF CHEMISTRY
COURSE TITLE: Basic Organic Chemistry
COURSE CODE: CHM 221, UNIT: 2.0.

AROMATICITY
Mechanism of Electrophilic Aromatic Substitution

Benzene resists reactions in which the aromatic pi cloud is lost. However, benzene undergoes a
series of reactions in which an atom or group of atoms replaces one of the ring hydrogen atoms.
These electrophilic aromatic substitution reactions result from the attack of an electrophile on
the ring and the substituent loss of a proton.

The intermediate complex -complex has several contributing structures distributing positive
charge over three of the five available p orbitals. These involve two equivalent carbons ortho to
the sp3 carbon and one para to that reference carbon.
Electrophilic aromatic substitution is believed to proceed by a bimolecular mechanism via the
formation of an intermediate, the rate-determining step (RDS). The three resonating structures
contributing to the intermediate are often combined; the whole reaction becomes:

Nitration: Benzene and conc. HNO3 reacts to produce nitrobenzene very slowly. The action of
conc greatly accelerates the rate. H2SO4. Aromatic nitrations are often carried in a mixture of
HNO3: H2SO4 (1:2) called mixed acid. The function of the sulphuric acid is to protonate the nitric
acid (which acts as a base towards sulphuric acid) and to increase the concentration of the actual
electrophile, the nitronium ion, NO2.
 Mechanism

There is much evidence that favours the existence and activity of the nitronium ion in mixed
acid. Nitronium tetrafluoroborate, a direct source of nitronium ion, readily nitrates benzene.

Alkylation: The simplest method of preparing alkylbenzenes is by reacting benzene with alkyl
halide in the presence of aluminium chloride. This reaction process is known as Friedel-Crafts
alkylation.

The initial step in the reaction is forming a complex between aluminium and the halide. This
complex possesses a highly polarized C-X bond.
Primary halide complexes undergo displacement of XAlCl3 by the benzene π system, while
tertiary halide complexes ionize and react by an SN1-like attack of the cation upon the π ectrons.

Acylation: Acylation (usually the chloride, RCOCl) react with benzene in the presence of excess
anhydrous aluminium chloride to produce a ketone (R-CO-C6H5). The usual solvent for these
acylations is either nitrobenzene or carbon disulphide CS2.

The initial step in this acylation reaction involves the formation of a complex between the
acylhalide and aluminium chloride. This then ionizes to produce the acylium ion RCO. Attach of
this acylium ion upon the benzene ring leads to the final product.
Sulphonation: The sulphonation of benzene can be accomplished by reacting with fuming
sulphuric acid (sulphuric acid containing dissolved sulphurtrioxide). The mechanism for this is
not so understood as that of nitration, it seems likely that the most important sulphonating agent
in fuming sulphuric acid is SO3.

The desulphonation of benzenesulphoric acid is achieved in the laboratory by heating the acid in
superheated steam, i.e. steam above 100 oC.
 The Effect of Existing Substituents on Electrophilic Aromatic Substitution

Substituents already present on a benzene ring may activate or deactivate the ring toward further
substitution. The influence of such substituents varies from wild to severe, depending largely
upon the substituent but to a smaller degree upon the specific electrophilic attacking the ring.
Any substituent upon the ring that places a positive charge (full or partial) on that ring will
deactivate the ring. The groups that can deactivate the benzene ring include: -NO 2,

-CF3, -SO3H, -NR3, and –CN.

On the other hand, groups that stabilize the developing charge in the activated complex or the
resulting complex activate the ring. Apart from the alkyl groups, the common activating groups
possess at least one non-bonding electron pair on that atom, which bonds the substituent to the
ring. Such groups include: -NH2, -OH, -OR, -NHR, -NR2.

Orientation:

The existing substituents on the benzene rings are classified as either O, P –directors (causing an
incoming substituent to attack ortho or para position to the existing substituent) or m –directors
(causing further substituent at the meta position).

The common O and P-directors are ring activators except for halogens. All m-directors are ring
deactivators. The halogens are O, P –directors but ring deactivators.

Ortho, Para Directors Meta Directors

Activating Deactivating
-OH -CN
-NH2, NHR, -NR -COOH
-OR -COOR
-NHC(O)R -CHO
-alkyl -COR
-aryl -NO2
Deactivating

-Halogens -NR3

-NR3

-SO3H
-SO2OR
Examples:

Experimental facts lead to the conclusion that while it is the inductive effect of the halogens that
dictates the deactivation of the ring; it is their ability to act as electron-pair donors that renders
them O, P –directors.
Some examples of the directive effect:
Synthesis of substituted benzenes:
In designing the synthesis of substituted benzene, it is important to consider the directive
influence of a substituent already on the ring. For example, chlorination of nitrobenzene
produces m-chloronitrobenzen, while nitration of chlorobenzene produces o- and p-
chloronitrobenzene produces o- and p-chloronitrobenzene.
Thus, starting with benzene, nitration must precede chlorination to yield the meta isomer but
must follow it to yield ortho or para isomer.

The following synthesis illustrates several points:

1. When the benzene ring contains two activating groups, the more powerful activator
controls the entry of a third substituent.
2. If a ring contains an activator and a deactivator, the activating group controls the entry of
a third group.
3. It is quite unlikely that two groups meta to one another will direct a group between them
regardless of their directing influence.
4. The reversibility of the sulphonation reaction provides a useful means of temporarily
blocking a position and introducing a deuterium onto a benzene ring.
The synthesis of 1,3, 5- trinitrobenzene (TNB) from TNT