BENZENE AND

ITS
DERIVATIVES
 INTRODUCTION

• An organic compound composed of six atoms of carbon joined in a ring and one

hydrogen atom attached to each carbon atom.

• Has the molecular formula C 6 H 6

• First isolated by Michael Faraday in 1825.

• Contained 92% carbon, and the relative molecular mass was found to be 78gmol -1 .
 Structure for Benzene

• Hydrogenation of cyclohexane was well known to be ΔH = -

119kJmol -1 .

• Comparable reaction would have liberated 360 kJmol -1 of heat.

• Exact value of benzene was found to be -208 kJmol -1 .

• Bond length of C-C bonds in benzene was found to be some way between that of an

alkane and alkene.

Bond Lengths lnm

C-C Cyclohexane 0.154

C=C Cyclohexane 0.134

C-C in Benzene 0.140

 Explanation of Structure

• Electron cloud was delocalized in benzene.

• Lower value of hydrogenation energies, equal C-C bond lengths.
 Characteristics of Benzene

• Benzene is a planar molecule with 6 carbons bonded in a planar ring with 120⁰ bond angle.

• All the carbons are sp 2 hybridized.

• Each carbon is covalently bonded to two other carbons and one hydrogen, forming a total

of three covalent bonds.

• Remaining outer electron of each carbon are shared with other carbons in the ring.

• Six electrons are thus delocalized around the ring system, giving extra stability.

• All bond lengths are the same.

Resonating structure of Benzene
Orbital diagram of Benzene
 Aromatic character and Huckel’s Rule

• Aromaticity in property of cyclic planar structures comprised of resonance bond

• Aromatic compounds are very stable, and do not break apart easily to react with

different substances.

• Huckel’s Rule (4n+2 rule)

 Criteria for Aromaticity

1. Molecule should be cyclic

2. Molecule should be planar

3. Molecule should be completely conjugated

(p-orbitals should be present on every atom in the ring)

4. The molecule must have 4n+2π electrons (n=0 or any positive integer)
 General methods of Preparation
1. Cyclic polymerization of alkynes

• Benzene is synthesized from ethyne by its cyclic polymerization when passed through

a red-hot iron tube at 873K.

 General methods of Preparation
2. Decarboxylation of aromatic acids

Preparation involves decarboxylation of the aromatic acids when heated with NaOH and

CaO (catalyst), to form benzene and sodium carbonate

 General methods of Preparation
3. Reduction of phenol

Reduction of phenol vapors in the presence of heated Zn dust produces benzene.

 Electrophilic aromatic substitution is the general method of the

production of products derived from benzene.

Reactions
of
Benzene
 Sulfonation

Reversible reaction that produces benzenesulfonic acid from benzene, upon the addition

of sulfur trioxide and fuming sulfuric acid.

 Mechanism
1. Addition of sulfur trioxide and fuming sulfuric acid (oleum), causes the sulfur to become

highly electropositive, as oxygen pulls away the electrons.

2. Benzene attacks sulfur, & benzenesulfonic acid is produced with subsequent proton transfer.
 Nitration

The first step in the nitration of benzene is to activate HNO 3 with H 2 SO 4 to produce

nitronium ion.
 Mechanism

Resonating forms of the intermediate can be seen in the generalized electrophilic

aromatic substitution.
 Halogenation

• The reaction with chlorine or bromine in also an electrophilic substitution

reaction that requires a catalyst.

• The catalyst is either aluminum bromide aluminum chloride, or iron.

 Halogenation
Chlorination

This reaction between benzene and chlorine occurs in presence of AlCl 3 or iron,

giving chlorobenzene.
 Halogenation
Bromination

This reaction gives bromobenzene by the reaction between benzene and bromine in

the presence of either iron or aluminum bromide.

 Mechanism
1. Formation of electrophile

2. Electrophilic substitution mechanism

 Friedel crafts alkylation

• Alkylation means substitution of an alkyl group onto something.

• For example – substitution of a methyl group to form toluene (methylbenzene).

Mechanism
Limitations of Friedel-Crafts alkylation reaction

1. Carbocation rearrangement – The carbocation tend to rearrange to gain

extra stability; hence certain alkylbenzenes can be synthesized.

2. Compound limitation – This reaction fails when used with strongly

deactivating compounds.

3. Polyalkylation – Products of this reaction are found to be much reactive

than the starting materials.

 Friedel crafts alkylation

• Used for synthesizes of the acylated benzene derivatives in the presence of

alkanoyl chloride and aluminum chloride as a catalyst.

Example
Mechanism
SUBSTITUENTS ON BENZENE
 Substituents on Benzene
The substituents on benzene ring can be considered as-
 Effect of substituents on the reactivity
Divided into two different groups based on the type of substituent that the ring carries.
 Effect of substituents on the reactivity
Divided into two different groups based on the type of substituent that the ring carries.
STRUCTURE AND USES OF BENZENE DERIVED
COMPOUNDS
 1. DDT (dichlorodiphenyltricholoroethane)

Uses –

• Most commonly used pesticide for insect control until 1972 in the USA.
• It was used to control malaria, body lice, typhus, and bubonic plague in the time of
World War II.
• It was used in a variety of food crops and was also used in buildings for pest control.
• It was found to be effective, with long duration of action and was cheap to
manufacture.
• It was banned due to increased resistance of pests and side effects on the human body.
 2. Saccharine

Uses –

• Used as a sweetener in vitamin supplements and medicines.

• Can be used as a substitute of sugar in baking industry
• It is an artificial sweetener that is used to sweeten the food and beverages
without calories.
• It gives additional stability and an improved taste. The cost of production is
lower, and several flavors are available.
 3. Benzene hexachloride

Uses –

• Important agricultural pesticide mainly used for the extermination of white

ants, leafhoppers, termites etc.
• It is commonly known as benzene hexachloride.
• The production was banned in 2009 due to side effects on human health.
 4. Chloramine

Uses –

• Used for disinfection of drinking water

• Used or swimming pool disinfection
• They are also used to improve the odor and flavor of water when chlorine is
used as a disinfectant.
• They are used to prevent biofouling in cooling water systems as well.