49 The Hydrocarbons

Benzene
Aromatic Hydrocarbon
Benzene C6 H6 (Phene)
The compound with pleasant smell are called aromatic compounds.
These compounds contain Benzene having ring of six carbon atoms, later on it was found that many compounds
we known resemble benzene in their structure but did not have any pleasant smell. So now the term aromatic
is not applied to compounds with pleasant smell but instead any compound which is benzene or which resembles
benzene in their chemical behaviour are called aromatic compounds.

Preparation
1. It was first isolated by Faraday from the cylinders of compressed illuminating gas obtained by the
pyrolysis of whale oil.
2. From Acetylene : Berthalot prepared benzene by passing acetylene through red hot tube.
Red Hot
3 CH CH
Iron tube
773 k
3. From Sodalime Decarboxylation
COONa
NaOH + CaO
+ Na2 CO3

4. From Phenol
OH
Zn dust
+ ZnO

5. From Chorobenzene
Cl
Ni-Al alloy
NaOH
+ HCl

6. From Benzene Sulfonic Acid

SO3H

+ H2O 150 200 C + H2SO4

Steam

7. From Benzene Diazonium Chloride

N2 Cl Sn Cl2/Na OH
+ HCl + N2
H2PO2
+ H3PO3 + HCl + N2

Structure of Benzene (Resonance Theory)
According to resonance theory, benzene is a resonance hybrid of two main Kekules structure (I) and (II).

I II III IV V

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Three other contributing structures called Dewars structures have less contribution towards the resonance
hybrid as one of the bond is very long which causes instability in structure. Thus, benzene is neither represented
by structure (I) nor by (II) but lies somewhere between the two Kekules structures.
A resonance hybrid is always more stable than either of two Kekules structures by 35 to 36 Kcal/mole. This
stabilization of benzene molecule is due to resonance and is called the resonance energy.
This resonance hybrid structure for benzene is supported by the following facts.
(i) Carbon-carbon bond lengths : According X-ray analysis and electron diffraction studies it is found
that all the carbon- carbon bond lengths in benzene are identical (139 pm). This bond length lies in
between carbon-carbon single (CC) bond length (154 pm) and double (C==C) bond length (134 pm).
So the character of bonds which link the carbon atoms in case of benzene is neither single bond nor
double bond but lies in between the two.
(ii) Resonance and stability of benzene : According to resonance theory, the energy of resonance
hybrid of benzene is less than any of the contributing structures by 35 to 36 kcal/mole. The resonance
energy of benzene can be calculated from the values of heat of combustion and heat of hydrogenation
as follows :
(a) Heat of hydrogenation : The heat of hydrogenation of a substance is the amount of heat evolved
when one mole unsaturated compound is hydrogenated. The heat of hydrogenation for each double
bond is 28.6 kcal/mole.

(Ni catalyst)
150 C ; H = 28.6 kcal/mole
Cyclohexene Cyclohexene

(Ni catalyst)
150 C ; H = 55.4 kcal/mole
1, 2- Cyclohexadiene Cyclohexene

(Ni catalyst)
150 C ; H = 49.8 kcal/mole
Benzene Cyclohexene
The addition of hydrogen to double bond is an exothermic reaction.
Heat of hydrogenation of benzene is 49.8 kcal/mole while the value expected on the basis of any
of Kekules structure is 85.8 kcal/mole. The difference of the two values gives the resonance
energy of benzene.
Thus, benzene structure is stable by 36 kcal/mole which is known as resonance energy of benzene.
36 kcal/mole of resonance energy is responsible for new set of properties known as aromatic
properties.
(b) Heat of combustion : Heat of combustion is defined as the amount of heat evolved when one
mole of the substance is completely burnt in excess of air or oxygen.
Heat of combustion values for CH bond, CC bond and C=C bond are 54, 49.3 and 117.4 kcal
respectively.
Contribution of 6 CH bonds = 6 54 = 324 kcal / mole
Contribution of 3 CC bonds = 3 49.3 = 147.9 kcal / mole
Contribution of 3 C=C bonds = 3 117.4 = 352.2 kcal / mole
Calculated value = 824.1 kcal / mole

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 51 The Hydrocarbons

Thus, heat of combustion of benzene calculated from any of the resonating structures is 824.1 kcal/mole
and experimentally observed value is 789.1 kcal/mole. It means resonance hybrid structure of benzene
has 35-36 kcal less energy than any of the Kekules structure which gives extra stability to benzene. For
this very reason, benzene undergoes substitution reaction readily rather than the addition reactions.

Orbital structure of benzene

The structure of benzene is best explained on the basis of molecular orbital concept. Each carbon atom in
benzene is in a state of sp2 hybridisation.
6 carbon atom each = 1s22s22px12py12pz0 (In ground state)
6 carbon atom each (In excited state) = 1s22s12px12py12pz1
The 2s and two of 2p (2px, 2py) orbitals of the excited carbon atom hybridise to form three hybrid orbitals of
equivalent energy and shape. The new orbitals are called sp2 hybrid orbitals. 2pz orbital, on each carbon atom
is left unhybridised and is perpendicular to the three hybridised orbitals which takes part in -bond formation.
Thus, the orbital picture of benzene showing the overlap of orbitals and formation of CC and C H bonds
is shown.
H H H H


C C C C


HC CH HC CH

C C C C

120
H H H H
(a) (b)
The net result is that there are two continuous hexagonal -electron clouds, one lying above and other below
the plane of the carbon atoms constituting the benzene ring.

Chemical Properties of Benzene

Benzene is very stable and is not affected by oxidising agents under ordinary conditions. The side chains
attached to benzene system are easily oxidised to carboxylic and group.
Through benzene consists of 3CC double bonds still it does not take part in addition reactions. This is due
to the extra stability which it attains due to resonance. Hence it fails to give addition itself i.e. does not
decolourizes alkaline KMnO4 or bromine water.
Benzene however undergoes substitution reaction
This is due to the fact that
(1) there are pool of electrons above and below the bonded carbon atom
(2) it acts as a source of electrons for electrophilic reagents.
(3) the aromatic character of benzene is preserved due to renonance stabilization.
The different electrophilic substitution reactions which benzene undergoes are
(1) Halogenation (2) Nitration (3) Sulfonation (4) Friedal Craft reaction.
1. Halogenation: Benzene reacts with chlorine or bromine at low temperature, in the absence of direct
sunlight but in the presence of halogen carrier to form chloro benzene or bromo benzene

Fe Br + HBr
+ Br2 50 C

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The Hydrocarbons 52

Cl
Fe or
+ Cl2 Fe Cl3 (310 - 320 K) + HCl

Iron fillings added to the reaction mixture reacts with Cl2 or Br2 to form FeCl3 or FeBr3 respectively.
The reactivity order is Cl2 > Br2. Reactions with Iodine is not possible as the reaction is reversible
and HI formed reduces iodo derivative back to reactants.
I

+ I2 + HI
Direct iodination is only possible in the presence of oxidising agents, like iodic acid, mercuric oxide
nitric acid etc which oxidise HI to iodine and moves the reaction in forward direction.
Mechanism:Any electrophilic substitution reaction involves three steps :
1. Generation of electrophile
2. Intermediate carbonium ion through -complex
3. Loss of proton.
1. Generation of Electrophile:
Lewis acid FeCl3 polarises the chlorine molecule to give highly reactive chloronium ion (Halonium)
Cl2 + Fe Cl3 Cl + FeCl4
2. Intermediate Carbonium ion through - compex
H Cl H Cl H Cl H E
+ Cl
+

Cl
3. Loss of Proton

The intermediate corbonium ion loses H+ ion to FeCl4 ion and thereby form chlorobenzene.

H Cl Cl
FeCl4 + HCl

Mechanism for Electrophilic Substitution Reactions

Any Electrophilic substitution reaction can be represented as
E
Lewis Acid
+EZ AlCl3 aldehyde
+ HZ

Step-I : Generation of Electrophillic

E Z + AlCl3 EAlCl3Z
This step is a fast step
Step-2 :Formation of Carbocation
E
+E
Transition state - complex
H E
E
Transition state - complex Benzenonium ion

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 53 The Hydrocarbons

This is the slowest step.

This benzenonium ion is resonance stabilized very similar to allylium carbocation.

H E H E H E H E

+

- complex

Step-3 :Loss of Proton

H E E

AlCl3 Z + HZ + AlCl3

The AlCl3 acts as a lewis acid

The formation of Arenium cations is the rate determining step
E H E
E H
T

TS-2
H 2
H 1

E
+E

+H
Hreaction

The confirmation of such a mechanism is supported by isotopic effect

KH
i.e. K D ratio

This could be as high as 2 to 8 if isotopic effect is present. The fact that isotopic effect is absent proves
that the C-H bond cleavage is not a part of rate determining step.
These electrophilic substitution reactions are irreversible because the energy barrier H2 for the reaction
of -complex to form products is less than H reactions for the reverse reaction of E (electrophile).Hence

K1 +
H E K2
Ar H + E (H+)
ArE
K 1 Ar

K2 > > > K1

Hence the reaction is irreversible.
2. Nitration: When benzene is reacted with a mixture of conc nitric acid and conc. HSO4 one gets
nitrobenzene.
NO2
H2SO4
+ HNO3 60 C

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At temperatures above 80C but below 120C one gets di-nitro benzene by using fuming HNO3 and
fuming HSO4
NO2
HNO3 + H2SO4

NO2
At very high temperature i.e. 120C and above trinitro product is obtained
Mechanism
(i) Generation of electrophillic
O

HO N O + H O S OH H2O N O + HSO4 H2O + NO2 + HSO4

O O O
(ii) Formation of carbocation

H NO2 H NO2

+ NO2 +

(iii) Loss of H+ ion

H NO NO2
2
+ HSO4 + H2SO4

3. Sulphonation: When benzene reacts with conc. H2SO4 (preferably fuming) at 80C we get benzene
sulfonic acid.
SO3H

+ H2SO4 + H2O

Mechanism
(i) Generation of electrophille
H2SO4 + H2SO4 H3O + SO3 + HSO4
(ii) Intermediate carbocation formation
H
SO3

+ SO3

(iii) Loss of Proton

H SO3 SO3H
SO3

4. Friedel crafts reaction

It is of two types : (a) Friedal Crafts alkylation (b) Friedal Crafts acylation.
(a) Friedal Crafts alkylation
Benzene reacts with alkyl halide in the presence of anhydrous aluminum chloride to form
alkyl benzene by the replacement of hydrogen atom of the nucleus by alkyl group. The reaction
is known as Friedel Crafts alkylation.
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 55 The Hydrocarbons

R
alkyl AlCl3
+RX

CH3
AlCl3
+ CH3 Cl

Mechanism
Methyl carbonium ion (CH3) is attacking electrophile in this mechanism and its formation is increased
in the presence of anhydrous AlCl3 catalyst. This mechanism involves the following steps :
(i) Generation of electrophille
+
CH3 CI + AlCl3 AlCl4 + CH3
Methyl carbonium ion

(ii) Intermediate carbonium ion formation.

CH3 ion is attacked by -electrons of the ring to form intermediate carbonium ion which is
resonance stablised.

H CH3 H CH3 H CH3 H CH3

+ CH

+ 3 +
- complex
I II III

(iii) Loss of Proton.

The intermediate carbonium ion loses H+ ion to AlCl4 ion to form methyl benzene (toluene).
H CH3 CH3

+ AlCl4 Fast + AlCl3 + HCl

Toluene
In case the alkylation is carried out with higher alkyl halide e.g., n-propyl chloride, then the electrophile
(CH3 CH2 CH2+) = propyl carbonium ion which is a primary carbonium ion rearranges to form more
stable secondary carbonium ion (isopropyl carbonium ion) and the main product formed will be isopropyl
benzene. This is explained as follows :
(i) Generation of electrophile.
+
CH CH2 CH2 Cl + AlCl3 CH3 CH2 CH2 + AlCl4
n - Proplyl chloride n - Proplyl carbonium ion

Hydride
+
CH3 CH CH2 CH3 CH CH3
Shift Secondary carbonium ion
H (More stable)
Primary
carbonium ion

Electrophile is CH 3 C H CH 3 ion and not CH 3 CH 2 C H 2
(ii) Intermediate carbonium ion formation.

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H3C CH3 H3C CH3 H3C CH3 H3C CH3

H CH H CH H CH
H CH
+ + +
+ H3C CH CH3 Slow +
+
I II III - complex

(iii) Loss of proton.

H3C CH3 H3C CH3

H CH CH

+ AlCl4 Fast HCl + AlCl3 +

(Isopropyl benzene)
(Cumene)

(b) Friedal Crafts acylation.Benzene can also react with acid chloride or acid anhydride in the
presence of anhydrous aluminium chloride to form aldehydes and ketones etc. by the replacement
of hydrogen atom of the nucleus by acyl group (RCO).The reaction is called Friedal Crafts
acylation.

AlCl3 (anlydrous) C R
+ R C Cl + HCl
O
O

O
H O
Anhydrous
C CH3
+ Cl C CH3 + HCl (Acetylation)
AlCl3
Benzene Acetyl chloride
Acetophenone

+ R C O C R Anhydrous C R
AlCl3 + RCOOH
O O O

O
H O
Anhydrous
C C6H5
+ Cl C C6H5 + HCl (Benzoylation)
AlCl3
Benzene Benzoyl chloride
Benzophenone

Mechanism :
The mechanism is similar to mechanism of alkylation and involves the following steps :
(i) Generation of electrophile.
O
Attacking electrophile R C (Acetyl carbonium ion) is given by acetyl chloride in the presence
of anhydrous AlCl3 which acts as a catalyst.
O O

CH3 C Cl + AlCl3 R C + AlCl4
Acetyl chloride Acetyl carbonium ion

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57 The Hydrocarbons

(ii) Intermediate carbonium ion formation.

O
Acetyl carbonium ion (CH3 C) attacks the the benzene ring to form intermediate carbonium
ion which is resonance stablised.

O O O
O
C R H C R H C R
H H C R
O
+ +
+O Slow
+ C R +
+
III - complex

(iii) Loss of proton. The intermediate carbonium ion loses H+ ion to AlCl4 ion to form acetophenone.

O O
H C R C R
+
+ AlCl4 + HCl + AlCl3

Acetophenone

The rate of reaction with different acylating agents is as given below.

(CH3)3C C Cl > (CH3)2 CH C Cl > CH3 COCl
O O
Addition Reactions
Benzene undergoes a number of addition reactions only under suitable conditions.
(i) Addition of hydrogen (Catalytic hydrogenation). Benzene adds on three molecules of hydrogen
when mixture is passed over finely divided Ni at 150200C under high pressure to form cyclohexane.

Ni
+ 3H2 150 200 C
Cyclohexane
(Hexahydrobenzene)

(ii) Addition of halogens. Benzene adds up three molecules of chlorine and bromine in the presence
of bright sunlight and in absence of halogen carries, forming benzene hexachloride and benzene
hexabromide respectively.

CHCl
CHBr
ClHC CHCl
BrHC CHBr
(i) Sunlight + 3Br2 (i) Sunlight + 3Cl2
ClHC CHCl
BrHC CHBr (i) Absence of (i) Absence of
halogen carrier halogen carrier
CHCl
CHBr Benzen hexachloride
Benzen BHC or Gammexane
hexabromide or Lindane or 666 or
Hexachlorocyclohexane

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The Hydrocarbons 58

(iii) Addition of ozone Benzene adds up three molecules of ozone forming glyoxal.
Zn/H2 O CHO
+ 3O3 3
CHO
Benzene Glyoxyal
(iv) Addition of CO (Gattermann Koch aldehyde synthesis)
AlCl
3
C6H6 + CO + HCl C6H5CHO + HCl
In this, the electrophile is formed as :
+
CO + HCl + AlCl3 H C = O + AlCl4
Electrophile

Oxidation
(a) Controlled oxidation :
As benzene is very stable, it does not react with oxidising agents like acidified potassium
permanganate and K2Cr2O7. When mixture of air and benzene vapours is passed over vanadium
pentaoxide (V2O5) catalyst at 500C, the nucleus breaks and gets oxidised to maleic anhydride,
Air / V2O5 CHCOOH
2 + 9O2 2 + 2H2O + 4CO2
500 C CHCOOH
Maleic acid
O
CH C
2 O + 2H2O
CH C
O
Maleic anhydride

Side chain on benzene ring can be oxidised to COOH group with alkaline KMnO4 solution or
acidified KMnO4 or acidified K2Cr2O7
CH3 O = COH
alk. KMnO 4
+ 3 [O] + H2 O
Toluene Benzoic acid

CH2 CH3 COOH

alk. KMnO4
+ 6 [O] + CO2 + 2H2O
Ethyl benzene

CH2 CH2 CH3 COOH

alk. KMnO 4
+ 9 [O] + 2CO2 + 3H2O
Ethyl benzene

Etards reaction
CH3 CHO
CrO2Cl2 / CCl4
Chromyl chloride
Toluene Benzaldehyde

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 59 The Hydrocarbons

CH2 CH3 CH2 CH3

CrO2Cl2 / CCl4

CH3 CHO
Acidified KMnO4
Acetic anhydride

(b) Complete Combustion. On burning in air or oxygen, benzene is oxidised to carbon dioxide and
water producing smoky flame.
15
C6H6(l) + O (g) 6CO2(g) + 3H2O(l) + heat
2 2
Miscellaneous reactions
1. Coupling reaction

700 800C
Red hot iron tube
Benzene Diphenyl

2. Chloromethylation
H CH2 Cl
ZnCl2
+ HCHO + HCl + H2O
Benzyl chloride

Effect of Substituent on Benzene Rings on Electrophilic Substitution

When further substitution is done on mono substituted benzene some groups. (alkyl group, halogen
group, OH group) direct the new entrant to ortho as well as para positions, other groups like, NO2, CHO,
COOH direct new entrant to meta position. Let us study this orientation and the directive influence of the
groups already present on benzene ring.

Type-I Directive influence of alkyl group : Consider toluene having methyl group present on the ring.
It is electron releasing group. The various possibilities of further substitution can be written as
follows :
Let us consider toluene and then determine the stability of the carbonium ion when new entrant
gets ortho, para and meta position.
CH3

Toluene
1. Ortho substitution
CH3 CH3 CH3
H H H

G G G

I III
II

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The Hydrocarbons 60

2. Para substitution

CH3 CH3 CH3

H G H G H G
IV V VI

3. Meta substitution
CH3 CH3 CH3

H H H
G G G
VIII
VII IX
Out of these carbonium ions (I) and (V) are particularly stable because the electron releasing alkyl
group is directly attached to carbon atom carrying the positive charge. This leads to dispersal of +ve
charge hence makes the carbonium ion more stable. Such a stable structure, does nto exist when meta
substitution takes place. Hence the carbonium ion formed for ortho and para and para substitution are
more stable, and are actually formed. Hence we say that whenever benzene contains an alkyl group,
further substitution, always occurs at ortho and para position.
Type-II Let us consider those compounds, in which benzene carries a group, containing a lone pair of
electrons e.g., aniline. The carbonium ions formed in these cases can be written as :
1. Ortho substitution
.. .. .. +
NH2 NH2 NH2 NH2
H H H H
G G G G

I II III IV

2. Para substitution
.. .. ..
NH2 NH2 NH2 NH2

H G H G H G H G
V VI VII VIII

3. Meta substitution
.. .. ..
NH2 NH2 NH2

H H H
G G G

X XI
IX
Out of these structures (IV) and (VIII) are particularly stable because in these cases the octet of
each carbon atom is complete. In case of carbonium ion for meta substitution such a structure is
not formed. Hence we say that the resonance hybrid for carbonium ion in ortho and para substitution
are more stable and are formed more easily. The further substitution in such compounds always
occur at ortho and para positions and not at meta positions.

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 61 The Hydrocarbons

Type-III Electron withdrawing groups i.e., NO2,COOH, CN etc. Consider case of nitro benzene.
O O
N

Nitrobenzene
When this compound, is attacked by an electrophile the carbonium ions which are formed for the
ortho, meta or para position can be written as follows :
1. Ortho substitution
O O O O O O
N N N
H H H
G G G

I III
II
2. Para substitution
O O O O O O
N N N

H G H G H G
IV V VI
3. Meta substitution
O O O O O O
N N N

H H H
G G G

IX X
VIII
Structure I and V are particularly unstable, because the NO2 group which is attached to the C
with positive charge helps to intensify the charge. Greater the intensification lesser is the stability.
Hence in the resonating structure for ortho and para substitution the resonance hybrid will be less
stable. The resonating structures, for meta substitution, make the hybrid more stable thus meta
substitution will be preferred. Whenever the electron withdrawing groups like NO2, COOH,
CN SO3H are present on the ring then the further substitution, will always occur at meta position.

Type-IV When halogen atom is present on the ring.

Consider chlorobenzene. Let us write various carbonium ions formed, when substitution takes
place at the ortho, meta and para position.
1. Ortho substituion
.. ..
: Cl : .. : Cl:
: Cl: : Cl:
H H H H

G G G G

III IV
I II

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The Hydrocarbons 62

2. Para substitution
.. .. ..
: Cl: : Cl: :Cl: : Cl:

H G H G H G H G
VI VII VIII
3. Meta substitution
.. .. ..
:Cl: : Cl: : Cl:

H H H
G G G

X XI
IX
Structures I and VI are particularly unstable, because electron attracting Cl atom is directly attached
to positively charged C atom. Thus positive charge gets intensified which leads to instability. On the
other hand structures IV and VIII are particularly stable, because the octet of each carbon atom is
complete. The contribution of structures IV and VIII are much more towards the resonance hybrids
as compared to structures VI and I, therefore, the destabilising effect of structures I and VI can be
neglected. Hence the hybrid for ortho and para substitution are stable. On the other hand there is no
resonating structure in meta substitution which is particularly stable. Hence we say that halogen
atoms always direct the new entrants towards ortho and para position.

Substitution in disubstituted benzene

In substituted benzene containing more than one substituent group, the substituents may either reinforce each
others directive ability, or they may oppose one another. In the case of an m-director versus an o,p-director,
remember that the meta substituent is also a deactivating group, while the o,p-director activates the ortho and
para positions with respect to the meta position. Thus the o,p-director will dominate the orientation of the
attacking electrophile.

CH3
1
Both are o,p-directors. Attack will occur at both 1 and 2
2
CH2CH3

CH3
1 3
CH3 is an o,p-director, NO2 is a m-director. Attack will occur at positions 1 and 2
4 NO2 and to a lesser extent at 3. Attack will not occur at 4
2

OCH3
1
OCH3 is an o,p-director, NO2 is a m-director. Attack will occur at position 1 only.

NO2

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