AROMATIC

HYDROCARBONS
 Aromatic
Hydrocarbons(Arenes)
The compounds containing one or more benzene
rings are aromatic compounds.
• eg: benzene, toluene,
naphthalene,

• Coal and petroleum

are the sources of
aromatic
hydrocarbons.
• There are some compounds which do not have benzene ring
yet they are aromatic.
 Characteristics of aromatic
compounds
• Are cyclic compounds with 5,6 or 7 membered ring
• Are planar molecules
• Have delocalized (4n+2)π electrons which are uniformly
distributed throughout the ring where n=0,1,2,3,4 etc.
• Are highly unsaturated but do not undergo addition
reactions easily.
• undergo electrophilic substitution reactions.
• burn with sooty flame as they have higher percentage of
carbon.
• do not give test for unsaturation
 Huckel’s Rule
• to be an aromatic compound , the compound must be cyclic,
planar with delocalized (4n+2)π electrons which are
uniformly distributed throughout the ring where
n=0,1,2,3......etc. This is known as Huckel rule of aromaticity.
eg: Benzene :
• hexagonal ring,
• planar,
• delocalized 6 π electron i.e (4n+2)π electron where n=1
• 4*1+2=6
 Derivatives of benzene
• Mono substituted benzene does not have isomer.
• Di substituted benzene exhibits positional isomerism. There exists
three different isomers:
• Ortho- , Para - , and meta – isomers

• 1, 2-sustituted 1,3-substituted 1,4-substituted

• Di substituted benzene isomers
 Preparations of Benzene
• 1) From phenol – benzene can be prepared from phenol by
heating with zinc dust.

• 2) From sodium salt of benzoic acid –sodium salt of benzoic

acid when is heated with soda lime, decarboxylation takes
place and forms benzene.

• sodium benzoate
• 3. From chloro benzene: chloro benzene when is reduced with
nickel aluminium alloy in presence of alkali benzene is formed.

• 4) From acetylene: acetylene when is passed through red hot

iron tube ,it gives benzene.
 Properties of Benzene
• Colourless liquid
• Immiscible with water but soluble in alcohol, ether etc.
• B.pt.80.40c freezing pt. 5.50C
• Vapour is toxic and carcinogenic.
• density less than water
 Chemical properties
1)Addition reactions:

Addition of chlorine: benzene adds with three molecules of

chlorine in presence of uv light to give benzene hexa chloride
(BHC).
• Addition of Hydrogen
• Benzene vapour mixed with Hydrogen when passed over
Nickel catalyst at 200-2500c gives cyclo hexane.
 Electrophilic substitution
reactions
• One of the important reaction of aromatic compounds is
elecrophilic substitution reactions.
• In this type of reactions Hydrogen atom from aromatic ring
gets substituted by electrophile from the reagent used.
• In benzene any of Hydrogen can be substituted by the
electrophile resulting mono substituted product.
• If the aromatic compound already has substituent in benzene
ring ,which of the hydrogen gets substituted depends on nature
of the substituent present in it whether it is electron releasing
or electron withdrawing substituent.
 Orientation of Electrophilic
Substitution in benzene derivatives
2) Electrophilic substitution reaction:
Substitution of hydrogen atom from benzene
ring by electrophile.
 Elecrophilic substitution reactions
• Halogenation
• Benzene reacts with halogen in presence of a Lewis acid to
give halo benzene.
• Example:
• Iodination of benzene:
• Iodination of benzene is carried out by reacting benzene with
iodine in presence of an oxidizing agent such as conc. HNO3
as HI formed as by product reduces iodo benzene into
benzene. An oxidizing agent oxidizes HI into iodine and helps
in iodination.
• Nitration:
• Benzene reacts with a mixture of conc.HNO3 and conc.H2SO4
at 600C to give nitrobenzene. The electrophile nitronium ion
(NO2+) is produced by the reaction between Conc.HNO3 and
conc. H2SO4 which substitutes H+ from benzene ring.
• Sulphonation
• Benzene reacts with fuming sulphuric acid ( a mixture of SO3
and conc.H2SO4) to give benzene sulphonic acid. The
electrophile in this reaction is HSO3+.
• SO 3 + H2SO4 HSO3+ + HSO4 -
• Friedel Craft’s alkylation
• It is the reaction in which H+ from aromatic ring gets
substituted by alkyl electrophile(R+) when the aromatic
compound is reacted with alkyl halide in presence of AlCl3 or
FeCl3 (a Lewis Acid).
• When benzene reacts with halo alkane in presence of Alcl3 it
gives alkyl substituted benzene.
• Production of electophile in Friedel craft reactions
• Alkylation

• Acylation

RCOCl + FeCl3 RCO+ + FeCl4-

• Friedel Craft’s acylation
• It is the electrophilic substitution reaction in which H+ of
aromatic ring gets substituted by the acyl electrophile (RCO+).

• The reaction is carried out by reacting aromatic compound

with acid chloride or acid anhydride in presence of anhydrous
AlCl3.
Benzene when reacts with acetyl chloride in presence of
AlCl3 it gives acetophenone.
• Combustion
• Benzene burns in air to give sooty flame.
Uses of Benzene
*V.imp
• Friedel craft’s alkylation:
Friedel craft’s alkylation reaction is an electrophilic substitution
reaction in which hydrogen atom of an aromatic compound is
substituted by alkyl electrophiles (R+). It is carried out by reacting
the aromatic compound with haloalkane in presence of anhydrous
AlCl3.
 Structure of benzene
• Benzene has molecular formula C6H6. it is possible to write
down open chain structure with this molecular formula as
below:
• CH2 = CH – C ≡ C – CH = CH2
• But benzene does not give positive test for unsaturation. And
it gives only one mono substituted product, if it is open chain
compound it can give more than one mono substituted
product.
• Benzene has homo cyclic hexagonal ring structure with
alternate double bond. Benzene can be represented with
following resonating structures.

• The actual structure is the hybrid of these structures.

• The structure cab be explained with molecular orbital picture.
• Each carbon of benzene is sp2 hybridized having three sp2
hybrid orbital. Out of these three sp2 orbital ,one overlap with
1s orbital of hydrogen and remaining two overlap with sp2
orbital's of two neighboring carbon atoms . This results C-H
single bond and C-c single bonds.
• As carbon is sp2 hybridized, each carbon has one un
hybridized p-orbital. These can overlap side wise resulting π
bond .
The sidewise overlapping can take place either way resulting two
resonating structures. It shows π bond is not localized. Thus in
benzene there is delocalization of π electrons.

The actual structure of benzene is hybrid of these two structures.

Hybridization of carbon
Shapes of hybridised
carbon molecules
State Huckel’s rule.
Give any two methods for preparation of benzene.
How would you convert benzene into i) BHC ii)
chlorobenzene iii) toluene?
What happens when
a) sodium benzoate is heated with soda lime?
b) benzene is reacted with ethanoyl chloride in
presence of anhydrous AlCl3?
A compound A (C7H6O2) reacts with NaOH solution
gives compound B. the compound B is heated with
soda lime gives compound C . The compound C is
reacted with chloromethane in presence of anhydrous
AlCl3 gives toluene. identify A, B and C.
• The molecular formula of a compound is C5H10. it may be branched
chain , straight chain or cyclic.
• a) Draw a displayed formula of C5H10 as a branched chain
hydrocarbon.
• b) pent-2-ene is a straight chain hydrocarbon with formula C5H10.
pent-2 –ene exhibit cis-trans isomerism.
i)what types of alkenes exhibit cis-trans isomerism and why?
ii)Draw cis- trans isomers of pent-2-ene with IUPAC names.
• c) draw the structural formula of two alcohols which would give the
above mentioned alkenes on dehydration.
• d) one of these alcohol exhibit optical isomerism. Draw the structural
formula of two isomers of this alcohol.