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4.4.3. Electrophilic Aromatic Substitution Reactions

The principal types of reactions involving aromatic rings are substitution, addition, and
oxidation. Of these, the most common are electrophilic substitution reactions. A summary of
the more critical substitution reactions of benzene is given below and includes halogenationꞏ,
nitration, sulfonation, alkylation, and acylation
Reaction name Reagents Electrophile M- that will A product formed
produced from abstract the H from benzene
the reagents in the last step
(p.62)
Br- Halobenzene aka
halogenation X2 and FeX3 X+ arylhalide e.g.
bromobenzene
H2SO4 and HSO4-
nitration HNO3 both NO2+ nitrobenzene
concentrated
sulfonation H2SO4 SO3 HSO4- Benzenesulfonic
acid
Friedel Crafts Alkyl halide X- Alkylbenzene e.g.
alkylation and AlCl3 R+ e.g. CH3+ - ethylbenzene
e.g. Cl
O X-
Friedel Crafts Acyl halide Acylbenzene, e.g.
acylation and AlCl3 e.g. Cl- acetophenone
R

Electrophilic aromatic substitution reactions involve stepwise processes with electrophilic

reagents. The critical step considers the attack of a double bond of the benzene ring on an
electrophile. It will then form a cationic intermediate. We may represent this step by the
following general equations in which the electrophile attacking reagent is represented either
as a formal cation, X + or as a polarised, neutral molecule.
STEP 1.

The intermediate depicted for aromatic substitution on the right-hand side above no longer has
an aromatic structure. It is an unstable cation with four π electrons delocalised over five
carbon nuclei, the sixth carbon being a saturated carbon forming sp3-hybrid bonds. It may be
formulated in terms of the following contributing structures, which are assumed here to
contribute virtually equally. (Note that the partial charges are at three positions, the two ortho
positions and the para position.)
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The dotted lines in the last structure on the right on the previous page ar incorrect. Please look
at the structures below for the correct version.
The dotted lines in the last two structures (also called resonance hybrids) on the right below
indicate where there are sometimes bonds present in a resonance form (three structures on the
left below) and sometimes not.

ACTIVITY 4.4.3.1
Add arrows to indicate how electrons move to form the first three structures (resonance forms)
on the left above.

STEP 2.
Loss of a proton from the intermediate results in regeneration of an aromatic ring yielding a
substitution product of benzene. The hydrogen atom that was initially in that position has now
been replaced by another atom.

Mechanism of electrophilic aromatic substitution:

M
E
H H

E draw all the resonance forms

H H

+ HM
H