CHEM 30121

THEORY OF ELECTROPHILIC AROMATIC SUBSTITUTION

Although the aromatic ring is a π-system, its chemistry is quite different from that of a simple
double or triple bond. Alkenes and alkynes undergo addition to the multiple bond when treated with
most electrophilic reagents. Typical reactions include addition of HX (X = halogen), addition of X2 (X
= Cl or Br), acid-catalyzed addition of H2O, hydroboration, etc. The process is usually exothermic
since π-electrons become lower energy σ-electrons when the multiple bond is destroyed. However,
the 6 π-electron system in an aromatic ring enjoys a special stability that makes addition reactions to
the ring very difficult. Instead, the aromatic ring prefers to undergo substitution during which a
hydrogen atom on the ring is replaced by another group thus preserving the aromatic nucleus in the
product. The scope of this class of reaction is very broad. Although a wide range of electrophilic
species and a variety of aromatic substrates are available, all of these reactions can be explained by
a common mechanism shown at the top of Scheme 1. In the first step, the electrophile attacks the
X X
X X E
E
E X
p-complex H E E
substituted benzene
a s-complex
X = EWG or EDG

E E E
5 6 5 6 5 6
4 1 4 1 4 1
X or X or X
3 2 3 2 3 2

X X X
H H H
E E E

H H H
E X E X E X

H H H
E E E
X X X

X X X
E

1,2-substituted 1,4-substituted E 1,3-substituted

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electron-rich aromatic ring to generate a π-complex that collapses rapidly to the σ-complex. The σ-
complex is a stabilized (conjugated) carbocation that loses a proton (deprotonation) in the last step
to restore the aromaticity in the final product.
If X = H in this equation, then the substrate is benzene and the product is a monosubstituted
aromatic ring. However, if X is a substituent group on the aromatic substrate, then the product is a
disubstituted benzene ring. Thus, there are three possible isomeric products from the reaction as
shown by the green, red, and blue structures at the bottom of Scheme 1. These products arise from
three different positions of attack by the electrophile on the aromatic ring. The route leading to the
green product (1,2-disubstituted or ortho isomer) involves a σ-complex formed by electrophilic attack
at either carbon 2 or carbon 6 of the substrate. The blue product (1,3-disubstituted or meta isomer)
is formed by electrophilic attack at either carbon 3 or carbon 5 of the substrate; and the red product
(1,4-disubstituted or para isomer) is the result of electrophilic attack at carbon 4. The group X on the
substrate determines which isomer(s) will be produced as the major product(s) in the reaction. For
example, if X is an electron-donating group, this can result in extra stabilization of the carbocation
leading to formation of both the ortho and the para products (i.e., X is an ortho/para director). On the
other hand, if X is an electron-withdrawing group, this can (but not always) destabilize the cation
leading to the ortho and para products and cause the meta isomer to the major product. These
groups are called meta directors.

H X = EWG H X = EDG H H
E X E X E X E X
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destabilizing stabilizing
resonance structure resonance structure

The electronic nature of the group X also has a dramatic impact on the reactivity of the ring.
If X is electron withdrawing (-NO2, -CN, -SO3H, carbonyl functions, etc.), the substrate becomes less
reactive that benzene toward substitution. If X is electron donating (alkyl, -OH, OCH3, -NH2, etc.),
the substrate is more reactive than benzene.
The most common electrophiles for electrophilic aromatic substitution include carbocations,
nitronium (+NO2), halonium (Cl+, Br+), +SO3H and acylium. Specific sets of reagents are used in the
generation of each of these electrophiles. For example, carbocations can be produced by at least
three familiar pathways. If a solution of isobutylene gas dissolved in benzene is treated with a very
strong mineral acid such as sulfuric acid, the protonation of isobutylene gives the t-butyl carbocation.
CH 3 CH 3
H
+ CH3
H2 C C H3 C C+
CH 3 CH 3 C CH3
AlCl3
CH3 CH3
(CH3 )3CCl H3 C C+
Friedel-Crafts CH3

+ CH3
H
(CH3)3 COH H3 C C+
(-H2O )
CH3

This cation attacks the benzene ring and gives t-butylbenzene as the product. The famous Friedel-
Crafts reaction uses t-butyl chloride and AlCl3 to generate the same carbocation. Finally, t-butyl

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alcohol with a strong acid is also a source of t-butyl carbocation via protonation of the oxygen and
loss of water.

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 PROBLEM SET – Electrophilic Aromatic Substitution

1. What is the role of acetic acid in the electrophilic aromatic substitution reaction you did in the
laboratory?
2. What is the structure of the most likely product from the reaction of methoxybenzene with an
excess of t-amyl alcohol under the same conditions you used in the laboratory? What other
products did you discount and why?
3. In the electrophilic aromatic substitution reaction, you did in the laboratory, the substitution of
the second t-amyl group on the ring is faster than the first substitution. Explain why this is
true.
4. Explain why the 1,4-product is the major product in the nitration of bromobenzene? Usually a
ration of ca. 2/3 (1,2-/1,4-product) is observed.
5. Provide a mechanism that explains why 4-bromonitrobenzene cannot be obtained by
bromination of nitrobenzene.