UNIT - 4 Huckel’s rule is applicable only if the compound meets

the following:
Aromatic Compounds &Aromaticity
✓ A cyclic structure.
Benzene and other organic compounds which resemble ✓ An unhybridised p orbital on each atom of the ring.
benzene in certain characteristic properties are called ✓ A planar or nearly planar structure.
aromatic compounds. These characteristic properties constitute

what is commonly known as aromatic character or Electrophilic Substitution in Benzene

aromaticity.
Electrophiles are positively charged species that are

For a compound to be aromatic, it must meet the attracted to an electron rich centre.

following criteria:
In benzene the electrophilic substitution reactions

✓ It must be a cyclic compound with some number of involving the following steps.

conjugated π bonds. Step 1

✓ Each atom in the ring must have an unhybridisedp Generation of the electrophile, E+

orbital.

✓ The structure must be planar or nearly planar.

Step 2
Huckel’s Rule
The electrophile (E+)attacks benzene and thus forms a
Huckel’s rule states that if the number of π electrons in σcomplex.
a compound is (4n+2), the compound is aromatic, if, it is

(4n)the compound is antiaromatic or nonaromatic. (n =

0,1,2,3,……)

This rule enables us to predict whether a given

compound is aromatic or antiaromatic.

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Step 3

Loss of a proton from the sigma complex to give the

final substitution product.

Step 2

The electrophile (NO2+) attacks benzene and thus forms

aσ complex.
Nitration

When benzene is treated with the mixture of

conc.HNO3and conc.H2SO4 (nitrating mixture) we get

nitrobenzene.

Step 3

Loss of a proton from the sigma complex to give the

final substitution product.

Mechanism

The mechanistic steps in the nitration of benzene can be

outlined as follows:

Step 1
Generation of electrophile.

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 Halogenation Step 2

Chlorination of benzene gives chlorobenzene, likewise The electrophile (Cl+) attacks benzene and thus forms aσ

bromination, iodination yields bromobenzene and iodobenzene complex.

respectively.

Step 3

Consider chlorination of benzene. Loss of a proton from the sigma complex to give the final

substitution product.

Mechanism

Step 1 Alkylation (Friedel-Craft’s Alkylation)

Generation of electrophile. It involves the reaction of an aromatic compound with

an alkyl halide to give the alkylated product. This reaction is

carried out in the presence of anhydrous aluminium chloride.

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Mechanism
Acylation (Friedel-Craft’s Acylation)
Step 1
It involves the reaction of an aromatic compound with

Generation of electrophile. an acid chloride (which produces acylium ion electrophile) to

give the acylated product. This reaction is carried out in the

presence of anhydrous aluminium chloride.

Step 2

The electrophile (CH3+) attacks benzene and thus forms

aσ complex.

Mechanism

Step 1

Generation of electrophile.

Step 3

Loss of a proton from the sigma complex to give the

final substitution product.

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Step 2 Naphthalene

The electrophile (CH3-CO+) attacks benzene and thus

forms aσ complex.

Preparation

1.From Petroleum

When petroleum fractions are passed over copper

catalyst at 690oC, naphthalene and methylnaphthalenes are

Step 3
formed.

Loss of a proton from the sigma complex to give the

Methylnaphthalenes are separated and converted into
final substitution product.
naphthalene by heating with hydrogen under pressure.

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2.From4-phenyl-1-butene Step 2

When 4-phenyl-1-butene is passed over red hot calcium β-benzoylpropionic acid is treated with amalgamated

oxide, naphthalene is obtained. zinc in the presence of HClto give γ-phenylbutyric acid.

(Clemmensen reduction)

3. By Haworth synthesis

This involves the following five steps:

Step 3
Step 1
γ-phenylbutyric acid is heated with conc.H2SO4to form α-
Benzene and succinic anhydride are heated in the tetralone. (Ring closure reaction)
presence of aluminium chloride to form β-benzoylpropionic

acid. (Friedel-Craft’s acylation)

Step 4

α-tetralone is heated with amalgamated zinc and HCl to

give tetralin. (Clemmensen reduction)

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Step 5
2.Sulphonation

Tetralin is heated with selenium to yield naphthalene.

Naphthalene undergoes sulphonation with conc.H2SO4 at
(Aromatization reaction)
60o C to form 1-naphthalenesulphonic acid.

If the reaction is carried at 165o C,2-

naphthalenesulphonic acid is obtained.

Properties

A. Electrophilic substitution reactions

1.Nitration 3.Halogenation

Naphthalene undergoes nitration with conc.HNO3 in the Naphthalene undergoes chlorination or bromination in
presence of sulphuric acid at 60o C to produce 1- boiling CCl4 to give 1-chloronaphthalene or 1-bromonaphthalene.
nitronaphthalene.

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 B. Other reactions

6. Reduction

Naphthalene undergoes reduction with sodium and

ethyl alcohol and gives 1,4-dialin or 1,4-dihydronaphthalene.

With sodium and isopentanol it gives tetralin or 1,2,3,4-

4.Friedel Craft’s acylation
tetrahydronaphthalene.

Naphthalene undergoes acylation with acetyl chloride

and aluminium chloride in carbon disulphide to give 1-

acetylnaphthalene. When nitrobenzene is used as a solvent, 2-

acetylnaphthalene is obtained.

Catalytic reduction hydrogenated both rings and

produces decalin or decahydronaphthalene.

5.Friedel Craft’s alkylation

Naphthalene undergoes alkylation with alkyl halides in

the presence of aluminium chloride to give 2-alkylnaphthalenes.

7. Oxidation

Oxidation of naphthalene with chromium trioxide in

acetic acid at room temperature gives 1,4-naphthaquinone.

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 4. Since the σ bonds results from the overlap of

trigonalsp2orbitals, all carbon and hydrogen atoms in

naphthalene lie in one plane. This has been confirmed

by X-ray diffraction studies.

Oxidation of naphthalene with oxygen and vanadium

pentoxide at 475o C yields phthalic anhydride.

5. Also each carbon atom in naphthalene possesses an

unhybridisedporbital containing one electron. These p

Structure orbitals are perpendicular to the plane containing the σ

bonds.
1. The molecular formula of naphthalene is C10H8
6. Naphthalene shows aromatic properties because it has
2. All the 10 carbon atoms in naphthalene are
(4n+2)πelectrons.
sp2hybridised.
3. The sp2hybridised orbitals overlap with each other and

with sorbitals of the 8 hydrogen atoms forming C-Cand

C-H σ-bonds.

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 Heterocyclic Compounds Properties

Heterocyclic compounds are cyclic compounds in which 1.Basic character

one or more of the ring carbons are replaced by another atom.
It is a weak base. It forms unstable salts with mineral acids.

The non-carbon atoms in such rings are referred to as

2.ElectrophilicSubstitution Reactions
hetero atoms.

(a)Nitration
The most common hetero atoms are N, Oand S.

Furan can be nitrated with a hot solution of nitric acid

E.g.
in acetic anhydride to form 2-nitrofuran.

Furan (b)Sulphonation

Furan may be sulphonated by sulphur trioxide in

Preparation
pyridine at 70o Cto yield furan-2-sulphonic acid.
By oxidation of furfural with potassium dichromate to

give furoic acid and subsequent decarboxylation at 200-300o C.

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(c)Halogenation 4.Ring-opening Reaction

Furan reacts vigorously with chlorine and bromine at When treated with methanol and hydrochloric acid,

room temperature to give polyhalogenated products, but does furan undergoes ring-opening forming the diacetal of

not react at all with iodine. succinaldehyde.

(d)Friedel-Craft’s Acylation

Use
Furan can be acetylated with acetic anhydride in the

presence of BF3at 0o Cto yield 2-acetylfuran. 1. Furan is used in the manufacture of tetrahydrofuran.

2. Furan serves as a diene in Diels-Alder reaction.

Thiophene

Preparation

3.Reduction
1.It is prepared by heating sodium succinate with phosphorous

Furan is reduced by hydrogen in the presence of nickel trisulphide.

to produce tetrahydrofuran.

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2.By distillation of furoic acid with barium sulphide. (c)Halogenation

Thiophene reacts vigorously with chlorine and bromine

at room temperature to give polyhalogenated products, but

does not react at all with iodine.

Properties

1.Electrophilic Substitution Reactions

(a)Nitration

Thiophene can be nitrated with a hot solution of nitric

acid in acetic anhydride to form 2-nitrothiophene.

(d)Friedel-Craft’s Acylation
(b)Sulphonation
Thiophene can be acetylated with acetic anhydride in

Thiophene may be sulphonated by conc.H2SO4 to yield the presence of H3PO3 to yield 2-acetylthiophene.

thiophene-2-sulphonic acid.

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2.Reduction Properties

Thiophene is reduced by sodium amalgam and ethanol 1.Electrophilic Substitution Reactions

to tetrahydrothiophene.
(a)Nitration

Pyrrole can be nitrated with a cold solution of nitric

acid in acetic anhydride to form 2-nitropyrrole.

Uses

1. Thiophenes are widely used as building blocks in many

agrochemicals and pharmaceuticals.

2. Hiophene displays coordination properties.

(b)Sulphonation
3. Thiophene can be fused with various heterocyclic

systems giving rise to various new heterocyclic systems Pyrrole may be sulphonated by sulphur trioxide in
with enhanced biological activity. pyridine at 100o C to yield pyrrole-2-sulphonic acid.

Pyrrole

Preparation

It is prepared by passing a mixture of acetylene and

ammonia through a red-hot tube.

(c)Halogenation

Pyrrole reacts vigorously with chlorine and bromine at

room temperature to give polyhalogenated products.

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 3.Reduction

Mild reduction of pyrrole with zinc and acetic acid

yields 3-pyrroline(2,5-dihydropyrrole). Catalytic reduction

completely hydrogenates the ring and produces pyrrolidine.

(d)Friedel-Craft’s Acylation

Pyrrole can be acetylated with acetic anhydride in the Uses

presence of BF3at 0o C to yield 2-acetylpyrrole.
1. Pyrrole and its derivatives are widely used as an

intermediate in synthesis of pharmaceutical medicines.

2. They are used as catalysts for polymerization process.

3. They are also used as corrosion inhibitors,

preservatives.

2.Oxidation

Pyrrole is oxidized by chromium trioxide in acetic acid

to give the imide of maleic acid.

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