Aromatic

compounds and
their chemical
reactions
CHAPTER FIVE
Chapter objectives:
Historicalbackground on aromatic
compounds discovery
Naming of benzene derivatives.
Study the structural principles of
aromatic compounds.
Chemical reactions of benzene
Introduction
 Faraday was the first to isolate benzene.
 Later german chemist synthesized benzene from
benzoic acid and showed that benzene has the
molecular formula C6H6
 Considering benzene’s high degree of unsaturation, it
might be expected to show many of the reactions
characteristic of alkenes and alkynes. Yet, benzene is
remarkably unreactive.
 Organic compounds from then were classified as
aromatic and aliphatic compounds
 The term aromatic refers to the fact that benzene and
its derivatives are highly unsaturated compounds that
are unusually stable toward reagents that react with
alkenes.
Naming of Benzene Derivatives
Rule (1): Many monosubstituted benzenes are named by
adding a substituent prefix to the word “benzene.

Rule (2): For other monosubstituted benzenes, the presence of

the substituent results in a new parent name(common name)
Rule (3): When two substituent are present their
position may be indicated by the prefixes
ortho, meta, and para (o, m and p) or by the
corresponding numerical positions:
Rule (4): With three or more substituents
on the benzene ring, numbers are used to
indicate their positions.
The lowest possible set of numbers should be
given to the substituents
 The substituents should be listed in
alphabetical order
 If one of the substituents defines a parent other
than benzene, this substituent defines the
parent name and should be designated
position 1
Rule 5:
 The C6H5- group is called phenyl
when it is a substituent
The phenylmethylene group is called
a benzyl (abbreviated Bn)
 A hydrocarbon with a saturated chain
and a benzene ring is named by choosing
the larger structural unit as the parent
 If the chain is unsaturated then it must be
the parent and the benzene is then a phenyl
substituent
The Structure of Benzene

 Kekulé was the first to formulate a reasonable

representation of benzene
 The Kekulé structure suggests a six membered ring with
alternating double and single carbon-carbon bonds and all
hydrogen atoms are equivalent.
 In fact, Spectroscopic methods have shown that
experimentally, the benzene molecule is a completely
symmetrical hexagon ,with equal C – C bond lengths of
1.39 Å, between the values found for the single bond
(1.47Å) and the double bond (1.34 Å)
 We now understand the surprising unreactivity of benzene
on the basis of two complementary descriptions, the
molecular orbital model and the resonance model.
Modern Theories of the Structure of Benzene
The Resonance Explanation of the Structure of Benzene
 Structures I and II are equal resonance contributors to
the real structure of benzene
 Benzene is particularly stable because it has two
equivalent and important resonance structures
 Each carbon-carbon bond is 1.39 Å, which is between
the length of a carbon-carbon single bond between sp2
carbons (1.47Å) and a carbon-carbon double bond (1.34
Å)
 the hybrid is represented by a circle in a hexagon (III)
The Molecular Orbital Explanation of the Structure of
Benzene
 The fact that the bond angle of the carbon atoms in
the benzene ring are all 120 ˚ strongly suggested that
the carbon atoms are sp2 hybridized.(planar
molecule, with p orbitals on all 6 carbons ) .
 The p orbitals overlap around the ring form a bonding
molecular orbital with electron density above and
below the plane of the ring.
 benzene is said to have a closed bonding shell of
delocalized П electrons because all of its bonding
orbitals are filled with electrons that have their spins
paired. This closed bonding shell accounts ,in part,
for the stability of benzene.
 Figure
Orbital overlap model of the bonding in benzene.
(a) The carbon, hydrogen framework. The six 2p orbitals,
each with one electron, are shown uncombined.
(b) The overlap of parallel 2p orbitals forms a continuous pi
cloud, shown by one a doughnut-shaped region above the
plane of the ring and a second below the plane of the ring.
How benzene reacts?
 As a consequence of the  electrons above and below
the plane of its ring, benzene is a nucleophile. It will,
therefore, react with an electrophile.
 Whenan electrophile attaches itself to a benzene ring, a
carbocation intermediate is formed.(two possibilities
)
 Consequently, benzene undergoes electrophilic
substitution reactions that preserve aromaticity, rather
than electrophilic addition reactions characteristic of
alkenes which would destroy aromaticity.
 This class of reactions includes substitutions by a wide
variety of electrophilic reagents.
 A General Mechanism for Electrophilic Aromatic Substitution:
Arenium Ion Intermediates
 Benzene reacts with an electrophile using two of its π
electrons (like an addition to an ordinary double bond)
 In step 1(the rate determining step because it is the
slowest step) Attack of the electrophile on the aromatic
ring to give a resonance-stabilized arenium ion.
 In step 2, Proton transfer to a base to regenerate the
aromatic ring: Unlike an addition reaction, the benzene
ring reacts further so that it may regenerate the very
stable aromatic system .
 The reactions we are about to study differ only in the way
the electrophile is generated and in the base that
removes the proton to re-form the aromatic ring.
• In step 1: (formation of arenium ion )

• In step 2: abstraction of a proton)

Nitration of Benzene

 Reagents Benzene reacts slowly with hot concentrated nitric acid to

yield nitrobenzene.
 Catalyst :The reaction is much safer and faster if it is carried out by
heating benzene with a mixture of concentrated nitric acid and
concentrated sulfuric acid (mixed acids).
 Electrophile Concentrated sulfuric acid increase the rate of the
reaction by increasing the concentration of the electrophile, the
nitronium ion (NO2+)
Halogenation of Benzene

Reagent and reactivities The reactivity of the halogens increases in

the order
Catalysts Halogenation of benzene requires the presence of a Lewis
acid
The Lewis acids most commonly used to effect chlorination and
bromination reactions are FeCl3, FeBr3 and AlCl3.
 Electrophile is X+
Sulfonation of Benzene

 Reagents :Sulfonation also takes place in concentrated sulfuric acid

alone, but more slowly.
 Benzene reacts with fuming sulfuric acid at room temperature to
produce benzenesulfonic acid.
 Fuming sulfuric acid is sulfuric acid that contains added sulfur
trioxide (SO3).
 Electrophile In either reaction the electrophile appears to be sulfur
trioxide.
 All of the steps are equilibria, including step 1, in which sulfur
trioxide is formed from sulfuric acid. This means that the overall is an
equilibrium, and therefore reversible as well.
Friedel-Crafts Alkylation

 Reagents and catalyst :An aromatic ring can be alkylated

by an alkyl halide in the presence of a Lewis acid
 Electrophile :the Lewis acid serves to generate a
carbocation electrophile.
 this substitution forms a new carbon–carbon bond.
Friedel-Crafts Acylation
 An acyl group has a carbonyl group attached to some R group, and a
reaction whereby an acyl group is introduced into a compound is
called an acylation reaction.
 Two common acyl groups are the acetyl group and the benzoyl
group

 Reagent and catalyst :The reaction is carried out by treating the

aromatic compound with an acyl halide in presence of a Lewis
acid. The product of the reaction is an aryl ketone..