KHONGO wa NGEGHAS Reactions of Aromatic Compounds

Electrophilic Aromatic Substitution

M.W. Kamiyango Premedical Sciences College of Medicine Malawi

Study Objectives
By the end of this lesson students should be able to:
Describe the mechanism of electrophilic substitution in

arenes using halogenation and nitration of benzene as examples.

Predict whether halogenation will occur in the side-chain in

arenes depending on reaction conditions.

Predict products for the oxidation of the side-chain in

arenes.
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Reactions of Benzene
Even though benzene is highly unsaturated it does not

undergo any of the regular reactions of alkenes such as addition or oxidation

Benzene can be induced to react with bromine if a Lewis

acid catalyst is present however the reaction is a substitution and not an addition
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Electrophilic Aromatic Substitution

Aromatic compounds undergo electrophilic aromatic

substitution (EAS) reactions

The electrophile involved has a full or partial positive charge.

A General Mechanism for Electrophilic Aromatic Substitution In step 1 of the mechanism, the electrophile reacts with two pi electrons from the aromatic ring to form an arenium ion (stabilized by resonance)

In step 2, a proton is removed and the aromatic system is

regenerated

Halogenation of Benzene
Halogenation of benzene requires the presence of a Lewis

acid

Fluorination occurs so rapidly it is hard to stop at

monofluorination of the ring

Iodine is so unreactive that an alternative method must be

used
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Mechanism of Benzene Bromination

Mechanism of Benzene Bromination

In step 1 of the mechanism, bromine reacts with ferric

bromide to generate an electrophilic bromine species

In step 2, the highly electrophilic bromine reacts with pi

electrons of the benzene ring, forming an arenium ion

In step 3, a proton is removed from the arenium ion and

aromaticity is regenerated The FeBr3 catalyst is regenerated

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Nitration of Benzene
Nitration of benzene is a reaction that results in the

introduction of a nitrogen dioxide (-NO2) group on a benzene ring.

Similar to halogenation, nitration is a substitution reaction

where a proton is substituted by an -NO2 group.

The electrophile involved is the nitronium ion (NO2+)

which is generated from a reaction between nitric acid and sulphuric acid.

Mechanism for the Nitration of Benzene

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Mechanism for the Nitration of Benzene

Sulfuric acid protonates the hydroxyl group of nitric

acid, allowing it to leave as water, forming a nitronium ion. Nitric acid is not the electrophile, it is a nitronium ion formed by protonation and dehydration of HNO3 by H2SO4. It is the nitronium ion the species that is attacked by the benzene. Loss of a proton from the sigma complex produces nitrobenzene.
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Reactions of Alkyl Benzenes

Alkyl benzene compounds are derivatives of benzene in

which at least one proton has been substituted by an alkyl group, e.g. Toluene:
CH3

Alkyl benzenes can undergo radical reactions in which the

carbon atom carrying the unpaired electron is on the side chain. Such radicals are easier to form because they are stabilized by resonance.
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Reactions of Alkyl Benzenes: Side Chain Halogenation

Alkyl benzenes undergo free-radical halogenation much more easily than alkanes because abstraction of a hydrogen atom at a benzylic position gives a resonance-stabilized benzylic radical.

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Oxidation of the Side Chain

Alkyl and unsaturated side chains of aromatic rings can be oxidized to the carboxylic acid using hot KMnO4

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