McMurry
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Chapter 16
Chemistry of Benzene:
Electrophilic Aromatic Substitution
Learning Objectives
(16.1)
Electrophilic aromatic substitution reactions:
Bromination
(16.2)
Other aromatic substitutions
(16.3)
Alkylation and acylation of aromatic rings: The
Friedel-Crafts reaction
(16.4)
Substituent effects in electrophilic substitutions
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(16.5)
Trisubstituted benzenes: Additivity of effects
(16.6)
Nucleophilic aromatic substitution
(16.7)
Benzyne
(16.8)
Oxidation of aromatic compounds
(16.9)
Reduction of aromatic compounds
(16.10)
Synthesis of polysubstituted benzenes
Worked Example
Monobromination of toluene gives a mixture of
Solution:
humans
Aromatic Nitration
Combination of concentrated nitric acid and
Aromatic Sulfonation
Occurs by a reaction with fuming sulphuric acid,
Aromatic Hydroxylation
Direct hydroxylation of an aromatic ring is
Worked Example
Propose a mechanism for the electrophilic
Worked Example
benzene ring
substitution is difficult
Polyalkylation occurs
carbocation electrophile
Mechanism of Friedel-Crafts
Acylation
Similar to Freidel-Crafts alkylation and also
biological pathways
Worked Example
Identify the carboxylic acid that might be used in
Worked Example
Solution:
Identification of the carboxylic acid chloride used
in the Friedel-Crafts acylation of benzene
involves:
Substituent Effects in
Substituted Aromatic Rings
Reactivity of the aromatic ring is affected
Substitution can result in an aromatic ring with a
higher or a lower reactivity than benzene
Worked Example
Predict the major product in the nitration of
bromobenzene
Solution:
Activating or Deactivating
Effects
Activating groups contribute electrons to the
aromatic ring
aromatic ring
Worked Example
Explain why Freidel-Crafts alkylations often give
Worked Example
Solution
An acyl substituent if deactivating
inductive effect
Worked Example
Explain why acetanilide is less reactive than
Worked Example
Solution:
Worked Example
Meta-Directing Deactivators
The meta intermediate possesses three
Worked Example
Draw resonance structures for the intermediates
Worked Example
Solution:
Trisubstituted Benzenes:
Additivity of Effects
Additivity effects are based on three rules:
The situation is straightforward if the directing
effects of the groups reinforce each other
Trisubstituted Benzenes:
Additivity of Effects
Trisubstituted Benzenes:
Additivity of Effects
Worked Example
Determine the position at which electrophilic
Worked Example
Solution:
Nucleophilic Aromatic
Substitution
Aryl halides with electron-withdrawing
Nucleophilic Aromatic
Substitution
Not very common
Uses
Nucleophilic substitutions
Favored by electron-
Favored by electron-
donating substituents
Electron-withdrawing
groups cause ring
deactivation
withdrawing substituents
Electron-withdrawing
groups cause ring
activation
Electron-withdrawing
groups are meta directors
ring
Electron withdrawing
groups are ortho-para
directors
Worked Example
Propose a mechanism for the preparation of
Worked Example
Solution:
Benzyne
On a general basis, there are no reactions
Benzyne
A Diels-Adler reaction occurs when
Benzyne
Benzyne has the electronic structure of a highly
distorted alkyne
Worked Example
Explain why the treatment of p-toluene with
Worked Example
Solution:
Oxidation of Aromatic
Compounds
In the presence of an aromatic ring, alkyl side
Oxidation of Aromatic
Compounds
Side-chain oxidation involves a complex
Worked Example
Mention the aromatic substance that is obtained
Worked Example
Solution:
Oxidation takes place at the benzylic position
Bromination of Alkylbenzene
Side Chains
Occurs when an alkylbenzene is treated with N-
bromosuccinimide (NBS)
Bromination of Alkylbenzene
Side Chains
The reaction of HBr with NBS occurs only at the
benzylic position
Worked Example
Styrene, the simplest alkenylbenzene, is
Worked Example
Solution:
Reduction of Aromatic
Compounds
Aromatic rings are inert to catalytic
Reduction of Aromatic
Compounds
Reduction of an aromatic ring requires either:
A platinum catalyst and a pressure of several
hundred atmospheres
A catalyst such as rhodium or carbon
Worked Example
Prepare diphenylmethane, (Ph)2CH2, from
Synthesis of Polysubstituted
Benzenes
Working synthesis reactions is one of the best
Worked Example
Synthesize m-Chloronitrobenzene from benzene
Solution:
Summary
There are two phases in an electrophilic
Summary
Resonance and inductive effects are the means