Preparation of Benzene :

1. Decarboxylation of sodium Benzoate

3.

From Phenol :

OH

4.

Zn

+ ZnO

From Sulphonic Acid :

HCl

SO3H + H2O

+ H2SO4

superheated steam

5.

Synthesis :
3C2H2

6.

Red hot tube

C6H6

From benene diazonium chloride :

NH2

NaNO2/HCl
o

0 C5 C

7.

Manufacture :
(a) n hexane :

CH3(CH2)4CH3

N+2Cl

H3PO2
Cu+

Al2O3 Cr2O3

600oC, Pressure

This is known as Hydroforming or catalytic Reforming or aromatization

(b)

Coal Tar :

Dry distillation
of wood

COAL TAR

fraction
distillation

Light-oil fraction
80 170oC

Physical properties of Arenes :

1.

Benzene and its homologues containing upto eight carbon atoms are colourless liquids with characteristic
smell.

2.

Due to large hydrophobic hydrocarbon part, arenes are not soluble in water but are soluble in organic
solvents.

3.

The melting points and boiling points of arenes increase with increase in the molecular size due to a
corresponding increase in the magnitude of van der Waal's forces of attraction. Amongst isomeric arenes, i.e.,
o-, m- and p-xylenes, the p-isomer is most symmetrical, has the highest melting point.

Reactions of Benzene :
1.

Addition Reactions :
(a) Of H2
3H2

(b)

Of O3
3O3

2.

Ni/200oC

Zn/H2O

3 OHC
CHO
Glyoxal

Oxidation :
Benzene is unreactive towards even strong oxidising agents such as : KMn04/K2Cr2O7. However in drastic
conditions, it can be oxidised slowly to CO2 and H2O. It can be burned (i.e., combustion) to give luminous and
smoky flame.

(a)

Controlled oxidation with air :

Benzene on oxidation with air at 773 K in presence of V2O5 as catalyst gives maleic anhydride.

9
+ O
2
(b) Oxidation of Alkyl Benzene :

Note : If R is a 3 alkyl group, then it resists oxidation.

3.

Substitution Reactions :
Most important reactions of benzene are electrophillic substitution reactions These are also denoted as SE
reactions.

The important electrophiles to be used here are.

Cl+(Chloronium ion), N+O2 (Nitronium ion),
SO3 (Sulphur trioxide), R+ Carbonium ion), R C = O (Acylium ion).
(a)

Hydrocarbon

Note:
(i)

In iodination, oxidising agents like HNO3 or HIO3 are used to neutralise HI, a reducing agent.

(ii)

In presence of sunlight and absence of halogen carriers (i.e., AlCl 3 , FeBr 3 , etc), benzene adds
three molecules of chlorine to form Benzene hexachloride (BHC) or Gammexane
hv
C6H6 + 3Cl2

C6H6Cl6
absence of halogen

b)

Nitration :

HNO3 (Conc.)

HNO3 + 2H2SO4
nitrating mixture
c)

55 60oC

H2SO4 (hot Conc.)

SO3
electrophile

2H2SO4

NO2
+ 2HSO-4 + H3O+
electrophile

SO3

+ H3O+ + HSO-4

Introduction of alkyl and acyl groups in presence of Catalysts :

AlCl3, FeCl3, SnCI4, SbCl3, Lewis acid or protonating agents like HF, H2SO4, H3PO4 etc.
(i)

NO2

Sulphonation :

(d)

H2SO4(conc)

Alkylation

RX

CH3Cl

AlCl3

AlCl3

RCI + AlCl3 AlCl4 + R+ (alkyl carbonium)

Note : The above reaction can be achieved with

R + HX

CH3 + HCl

SO3H + H2O

(a)
(b)

ROH in HF or dil H2SO4

RCH = CH in HF or dil. H2SO4

CH3

CH3

+ H3C C OH

H2SO4 (dil)

C CH3
CH3

CH3

CH3

H3 C
C = CH2

H2SO4 (dil)

C CH3
CH3

H3C

(ii)

Acylation :

COR

+ R COCl
Acyl chloride
O

RCOCl + AlCl 3

R C + AlCl 4+
Acylium

+ HCl

The above two reactions are called as Acetylation and Benzoylation respectively.
Some Friedal Craft acylation and alkylation are shown below.

Note:
(i) Aryl and vinylic halides cannot be used in Friedal craft reactions as they do not form carbocations easily.

+ H2C = CHCl

AlCl3

No reaction

(ii) In substituted benzenes, Friedal Craft reactions gives poor yield when electron withdrawing
(de-activating) groups are present on the ring. These include:

O
+

N O 2 , N (C h 3 ) 3 , C O O H ,
(iii)

C R , C F 3, S O 3H

In Friedal craft alkylation most stable carbocation (from alkyl alide or alkene) determines the final

substitution product. It does not give n-propyl benzene since CH3 - CHCH3, being a 2 carbocation is more
stable.

(b)

CH3 group being o and p directing directs incoming electrophile to o and p position :