Benzene and Aromatic Compounds

• Benzene (C6H6) is the simplest aromatic hydrocarbon (or arene).

• The resonance description of benzene consists of two equivalent Lewis
structures, each with three double bonds that alternate with three single
bonds.
• The true structure of benzene is a resonance hybrid of the two Lewis
structures, with the dashed lines of the hybrid indicating the position of the
 bonds.

• Because each  bond has two electrons, benzene has six  electrons.

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• In benzene, the actual bond length (1.39 Å) is
intermediate between the carbon—carbon single bond
(1.53 Å) and the carbon—carbon double bond (1.34 Å).

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Nomenclature of Benzene Derivatives
• To name a benzene ring with one substituent, name the substituent and add
the word benzene.

• Many monosubstituted benzenes have common names which you must

also learn.

• There are three different ways that two groups can be attached to a benzene
ring, so a prefix—ortho, meta, or para—can be used to designate the relative
position of the two substituents.

ortho-dibromobenzene meta-dibromobenzene para-dibromobenzene

or or or
3o-dibromobenzene m-dibromobenzene p-dibromobenzene
or 1,2-dibromobenzene or 1,3-dibromobenzene or 1,4-dibromobenzene
• If the two groups on the benzene ring are different, alphabetize the names of the
substituent preceding the word benzene.
• If one substituent is part of a common root, name the molecule as a derivative of that
monosubstituted benzene.

• A benzene substituent is called a phenyl group, and it can be abbreviated in a structure as “Ph-”.

• Therefore, benzene can be represented as PhH, and phenol would be PhOH.

• The benzyl group, another common substituent that contains a benzene ring, differs from a phenyl
group.

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Stability of Benzene
• Consider the heats of hydrogenation of cyclohexene, 1,3-cyclohexadiene and
benzene, all of which give cyclohexane when treated with excess hydrogen in the
presence of a metal catalyst.

• The low heat of hydrogenation of benzene means that benzene is especially stable. This
unusual stability is characteristic of aromatic compounds.
• Benzene’s unusual behavior is not limited to hydrogenation. Benzene does not undergo
addition reactions.
• Benzene does not react with Br2 to yield an addition product.

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The Criteria for Aromaticity—Hückel’s Rule
Four structural criteria must be satisfied for a compound to be aromatic.

[1] A molecule must be cyclic.

To be aromatic, each p orbital must overlap with p orbitals on adjacent atoms.

[2] A molecule must be planar.

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[3] A molecule must be completely conjugated.
Aromatic compounds must have a p orbital on every atom.

[4] A molecule must satisfy Hückel’s rule, and contain a particular number of 
electrons.
Hückel's rule:
An aromatic compound must contain 4n+2π electrons [n (integer no.) =
0, 1, 2, and so…]
Benzene is aromatic and especially stable because it contains 6  electrons. Cyclobutadiene
is nonaromatic and especially unstable because it contains 4  electrons.
Benzene
Cyclobutadiene
An aromatic compound
non-aromatic compound

4n+2= 6 e 4n+2=4 e
4n=6 - 2=4 4n= 4 - 2 =2
n=4/4=1 n=2/4 = 1.5
7 aromatic non-aromatic
Note that Hückel’s rule refers to the number of  electrons,
not the number of atoms in a particular ring.

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Examples of Aromatic Rings
• Completely conjugated rings larger than benzene are
also aromatic if they are planar and have 4n + 2 
electrons.
• Hydrocarbons containing a single ring with alternating
double and single bonds are called annulenes.
• To name an annulene, indicate the number of atoms in
the ring in brackets and add the word annulene.

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• Thus, although five resonance structures can also be drawn for the
cyclopentadienyl cation and radical, only the cyclopentadienyl anion
has 6  electrons, a number that satisfies Hückel’s rule.

Indicate which of the following are aromatic and non-aromatic?

B
A

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 Resonance of Benzene

The oscillating double bonds in the benzene ring are explained with the help of resonance structures
as per valence bond theory. All the carbon atoms in the benzene ring are sp2 hybridized. One of the
two sp2 hybridized orbitals of one atom overlaps with the sp2 orbital of adjacent carbon atom
forming six C-C sigma bonds. Other left sp2 hybridized orbitals combine with s orbital of hydrogen
to form six C-H sigma bonds. Remaining unhybridized p orbitals of carbon atoms form π bonds with
adjacent carbon atoms by lateral overlap.

This explains an equal possibility for the formation of C1 –C2, C3 – C4, C5 – C6 π bonds or C2 – C3,
C4 – C5, C6-C1 π bonds. The hybrid structure is represented by inserting a circle in the ring as
shown below in the figure. Hence, it explains the formation of two resonance structures proposed by
Kekule.

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 Preparation of benzene

1. From ethyne ( manufacture of benzene) :

When ethyne gas is passed through a red hot iron or

copper tube, the three molecules of ethyne (acetylene)
polymerize to give benzene.

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 2. By decarboxylation of sodium salt of benzoic acid (
Laboratory method):

Benzene can be prepared by heating sodium salt of

benzoic acid ( i.e. sodium benzoate) with sodalime. This
reaction is called decarboxylation reaction.

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 3. By reducing phenol with zinc :

When vapours of phenol are passed over heated zinc dust, benzene
is produced.

preparation of benzene from phenol

4. By the reduction of aryl halides :

Benzene can be prepared by the reduction of haloarene with

nickel – aluminium alloy in the presence of alkali.

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 Physical Properties of Benzene

The various properties of benzene are mentioned below:

❖ Benzene is immiscible in water but soluble in organic solvents.

❖ It is a colourless liquid and has an aromatic odour.

❖ It has a density of 0.87g cm-3. It is lighter than water.

❖ Benzene has a moderate boiling point and a high melting point.

(Boiling point: 80.5°C, Melting point: 5.5°C)

❖ Benzene shows resonance.

❖ It is highly inflammable and burns with a sooty flame.

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Chemical properties of benzene

Electrophilic substitution reactions of benzene

The most important/common reaction of benzene is electrophilic substitution
reaction. In this reaction, an electrophile attacks the benzene and substitutes
one of the hydrogen atoms of benzene ring. Eg.

1. Halogenation :

Benzene reacts with bromine in presence of ferric bromide as catalyst to give

bromobenzene.

Similarly, chlorine reacts with benzene in presence of ferric chloride or

AlCl3 as catalyst to give chlorobenzene.

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 2. Nitration : When benzene is heated with conc. HNO3 in the presence of conc. H2SO4 at about 600C
gives nitrobenzene.

3. Sulphonation : When benzene is heated with conc. H2SO4 , benzene sulphonic acid is formed.

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 4. Friedel – Craft’s reaction :

• Friedel Craft’s alkylation : Introduction of an alkyl group ( – R ) in the benzene ring by treating
benzene with an alkyl halide (R-Cl or R-Br) in the presence of anhydrous AlCl3 is known as
Friedel- Craft’s alkylation. Eg.

• Friedel Craft’s acylation : Introduction of an acyl group (i.e. keto group) ( RCO- ) in the benzene
ring by treating benzene with an acylating agent like acid chloride (RCOCl) or acid anhydride in
the presence of anhydrous AlCl3 is known as Friedel- Craft’s acylation. Eg.

Similarly, benzene when treated with benzoyl chloride in the presence of anhydrous AlCl3 gives
18 benzophenone.
 Addition reactions of benzene

Because of unusual stability of benzene ring( due to delocalization of π – electrons), addition

reactions are difficult to take place. However due to presence of three double bonds, under
proper condition (drastic condition)(i.e high temperature and pressure) addition reaction takes
place.

• Addition of hydrogen : When benzene vapour is heated with hydrogen gas in presence of
nickel or platinum catalyst, cyclohexane is formed.

• Addition of halogen : Benzene adds three molecules of chlorine in presence of sunlight ( UV

light) to give benzene hexachloride (BHC).

BHC is extensively used in agriculture as pesticide under the trade name gammexane or
lindane or 666.
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Combustion reaction of benzene

Benzene burns in air with sooty flame to give carbondioxide and water.

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 Uses of benzene
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❑ It is used as a starting material for the preparation of varieties of

aromatic compounds which are used for the manufacture of dyes,

drugs, perfumes, explosives, etc. ( Eg. benzene is used for making

toluene which is needed for making TNT.)

❑ It is used as a solvent for the extraction of fat and oil.

❑ It is used as a fuel for automobiles in the name of benzol. {It is used

in gasoline to increase the octane rating of gasoline.}

❑ It is used for dry cleaning of woolen clothes.

❑ It is used for making phenol needed for producing Bakelite.

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