BENZENE CHEMISTRY

BENZENE
Br Br
Br Br
Aromatic Compounds
 Aroma - Pleasant odour-burns with sooty flames.
Br
 The aromatic compounds which contain 1,2,3-Tribromo benzene 1,2,4- Tribromo benzene
Benzene ring are called Benzenoid compounds Cl COOH

 Benzenoid compounds include benzene, its

derivatives and polynuclear hydrocarbons such O2N NO2 O2N NO2
as naphthalene, anthracene, biphenyl, etc. 3, 5-dinitrobenzoic acid
CH2 – CH2 – CH2 – CH3 OH
 The aromatic compounds which do not contain
Benzene ring are called non-benzenoid
compounds. n-butyl benzene Hydroxy benzene Nitro Benzene
(phenol or Carbolic acid) (oil of mirbane)
Nomenclature : (The names written in brackets are common
names which are frequently used.)
 In these compounds the substituent name is  When two substituents are present, their relative
placed as prefix to the word benzene positions are indicated by the prefixes ortho, meta
or para(o-;m-;p). These prefixes are only for
disubstitued compounds but for more substituted
OCH3 CH3 Cl compounds numbers are given
Cl
NO2
COOH

Methoxy benzene Methyl benzene Chlorobenzene

(anisole) (toluene) Cl
1,4-Dichlorobenzene 2-Nitrobenzoic acid
OC2H5 CH3 CH3 (para-dichlorobenene) (o-nitrobenzoic acid)
CH3
CH3 – C = CH – CH3 CH3 – C = CH – CH3

CH3 C6H5
Ethoxy benzene 1,2 - dimethyl benzene 1,3 - dimethyl benzene 2-phenyl-2-butene
(Phenetole) (o-xylene) (m-xylene) Cl
2(3-clorophenyl)-2-butene
CH3 CH3 CH3 ARYL GROUPS
CH CH3
CH2 –

CH3 CH3 (or) C6H5 – CH2 –

CH3
1,4 - dimethyl benzene Iso propyl benzene
Mesitylene Benzyl
(p-xylene) (Cumene)
 C6 H 5  group is known as phenyl ,which is some
 Position of more than two substituents are always
times abbrevated as Ph or  .
indicated by numbers

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 CHEMISTRY BENZENE
CLASSIFICATION OF AROMATIC QUASI AROMATIC COMPOUNDS
COMPOUNDS  Polar aromatic compounds are called quasi
Aromatic compounds aromatic campounds.
 

Homo / Carbo cyclic Hetero cyclic Ex:

Benzenoid Non-Benzenoid
POLYCYCLIC AROMATIC
BENZENOID COMPOUNDS COMPOUNDS
These compounds contain only benzen rings in  These hydrocarbons contain two or more benzene
their rings. Ex: Benzene, Naphthalene, etc. rings .These are further divided into two classes.
NON BENZENOID COMPOUNDS a)Those which contain isolated benzene rings .
These compounds do not contain benzene rings.
examples are :

CH2

Diphenyl Diphenyl methane

Calicene b) Those in which two or more benzene rings are
O O fused or condensed. Examples are
OH

Tropone Tropolone Naphthalene Anthracene

HOMOCYCLIC AROMATIC
COMPOUNDS
If the aromatic rings contain only carbon atoms
in their ring then they are called carbocyclic or
homo cyclic compounds
Ex: Benzene, nepthaline, anthracine
HETERO CYCLIC AROMATIC Phenanthrene
COMPOUNDS RESONANCE THEORY
 Aromatic compounds with Heteroatom like  The phenomenon in which two or more structures
B,N,O,S etc in their ring are called hetero cyclic can be written for a molecule but none of them
compounds. represents its actual structure is called resonance.
 Various possible alternative structures are known
as resonating structures or Canonical structures.
N O S  In these structures only delocalization of 
H electrons takes place.
Pyridine Pyrrole Furan Thiophene
 During this delocalization some energy is released
N which is called resonance energy.
N  Greater the resonance energy greater will be the
NH stability.
N N N
H  More the number of resonating structures or
Quinoline Indole Purine canonical structures more will be the stability.

Narayana CO Programme CO Spark IIT - JEE 249

 BENZENE
 For benzene resonance energy is 36 K.cal/mole
or 150.48 KJ/mole.
 According to Kekule, Benzene is resonance
hybrid of two structures, which differ in the
position of double bonds.
CHEMISTRY
REASONANCE ENERGY
Potential energy defference between the most
stable resomating structure and real structure
(reasonance hybrid) is called as reasonance
energy. It has a fixed value for a molecule.

 Kekule structures are far more stable than the Potential Most stable resonating
Dewar’s structures. Thus these two Kekule energy
structures contribute more to resonance hybrid Resonance energy
(80%) than the rest of the structures.
Resonance energy

Structures of benzene

Dewar's structures (20%) The reasonance energy can be calculated by

hydrogenation reaction
 Since, the two Kekule’s structures are equivalent
Pt
the stability of the resulting resonance hybrid is +H2
very high. Due to resonance each C-C bond in
Cyclohexene Cyclohexane
benzene has some double bond character and
this has been confirmed by measuring bond length ; H 28.6k cal mol1
between two adjacent carbon atoms in various
compounds of benzene. Pt
+H2
 The bond length C-C (single bond as in ethane)
is 1.54 Ao and C=C (double bond as in ethene) 1,3 - cyclohexadiene
is 1.34Ao. The carbon to carbon bond length in
benzene has been found to be 1.39 Ao , which H  55.4k cal mol 1 (almost double that of
indicates C-C bond length in benzene is in cyclo hexene)
between single and double bond lengths.  If benzene were a cyclohexatriene then the energy
 Resonance can occur in a molecule if it is planar. to be liberated in hydrogenation is
Thus, all the C and H are expected to be planar. 3  28.6  85.8 k .cal.mole 1 but actually only
Instead of using two Kekule’s structures, the
hybrid is represented for the sake of convenience 49.8 k cal is liberated. To the extent of
only, by one structure as shown below (Actually 85.8  49.8  36 k .cal / mole
the hybrid form cannot be represented on paper) Example:
Compound Resonance energy in kcal/mol
Benzene 36 kcal/mol
Resonance hybrid of benzene. Naphthalene 61 kcal/mol
phenanthrene 84 kcal/mol

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 CHEMISTRY BENZENE

STRUCTURE OF BENZENE
 Experimental results and analytical data reveals Aromatic Anti Aromatic Non - aromatic
Cyclic Cyclic Cyclic
the molecular formula of benzene as C6 H 6 . 2 2
Planar (sp ) Planar (sp ) Non - planar
 The carbon to hydrogen ratio indicates
Completely Completely
unsaturation in the molecule. Conjugated system Conjugated system None
 But benzene does not behave like other –1
(4n +2)e is
–1
(4n)e is
None
unsaturated compounds (alkenes, alkynes.) stable unstable
 It does not decolourise
a) Br2 water (or) alkaline KMnO4 Stability Order :
Aromatic > non aromatic > anti aromatic
b) It can't undergo Polymerisation and oxidation Energy Order :
under normal conditions Anti aromatic > non aromatic > aromatic
c) It undergoes electrophilic substitution
ILLUSTRATIVE EXAMPLES
reactions rather than addition reactions and is a
Benzene
stable molecule.
 The stability and the structure of benzene have
been explained on the basis of two modern It has 6  electrons
theories.
1) Resonance or valence bond theory 4n+2=6 and here n=1.
2) Molecular orbital theory  Aromatic
ORBITAL MODEL OF BENZENE Naphthalene
 Benzene is hexagonal planar. All the six carbon
atoms undergo sp2 hybridisation. It has 10  electrons
 In Benzene each carbon is surrounded by three
sp2 hybridized orbitals and one unhybridized ‘P’ 4n + 2 = 10 and hence n = 2.
 Aromatic
orbital with unpaired electron.
Anthracene
 The six unhybridised ‘p’ orbitals form three
delocalised  bonds by side wise overlapping It has 14  electrons
 In Benzene the total number of hybridized orbitals
and pure orbitals are 18 & 12 respectively.
4n + 2 = 14 and hence n=3
 The total number of  and  bonds in benzene  Aromatic
are 12 & 3 Cyclopentadienyl anion
 The Bond angle is 1200 and the bond length is
1.39 Ao. This is due to delocalisation of
It has 6  electrons
'pi'electons (or) resonance.
 The C-C bondlength (1.39A) is intermediate 4n + 2 = 6 and hence n=1.
between C-C single bond (1.54 A0) and C = C  Aromatic
double bond (1.34A0) length. Cycloheptatrienyl cation
AROMATICITY
According to huckel’s rule, monocyclic, planar
It has 6  electrons
conjugated system with (4n+2)  e  are aromatic
4n + 2 = 6 and hence n=1.
those with 4n  e  are Anti-Aromatic, n=integer

Narayana CO Programme CO Spark IIT - JEE 251

 BENZENE CHEMISTRY
Cyclopropenyl cation W.E-2: Which of the following compounds is
more acidic ?
It has 2  electrons
(or)
4n + 2 = 2 and hence n=0.
(a) (b)
2  electrons,no conjugation Sol: By releasing H  in (a), the anion becomes
Cyclopropene aromatic and hence compound (a) is more
 Non aromatic acidic than (b).
PREPARATION OF BENZENE

4 e i.e 4n e  i ) BY DECARBOXYLATION OF
BENZOIC ACID
n 1  Sodium benzoate on heating with soda lime gives
Cyclobutadiene
 Antiaromatic benzene. It is a laboratory method of preparation.
Note :  electrons are not delocalised COONa

 4n  2  e  6 + NaOH
CaO
Heat
+ Na2CO3

Cyclo butenyl dianion

n 1
 Aromatic Sod.Benzoate
+ COOH
2 Cao
+ 2CaCO3

4ne  4  COOH
n 1 Phthalic acid
Cyclo pentadienyl cation ii) FROM ACETYLENE
 Anti aromatic (POLYMERISATION)
 On passing acetylene gas through red hot iron or
copper tube, benzene is formed.
 4n  2    10
n2 3C2H2 600ºC
Azulene Cu
 Aromatic

– Non aromatic CH3 – C  CH

Hot Fe

It has one sp3 cabon atom  Non-Aromatic Mesitylene
QUASI AROMATIC COMPOUNDS
W.E-1: Explain whether the compound shown
Hot Fe
below is aromatic or not ?  2-Butyne

Hexa Methyl Benzene

iii)
Sol: The compound has one 5 membered and one 3 
membered ring. Five membered ring contains 6
electron and three membered ring contains 2
electrons. Hence the compound shown is
aromatic
AROMATISATION
When straight chain alkanes which contian 6 or
more than 6 carbon atoms passed over redhot
V2O5  or  Mo2O3  or  Cr2O3 , etc. aromat ic
compounds are formed

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 CHEMISTRY BENZENE
NH2 N2Cl
Cr2O3 + Al2O 3
CH3CH2CH2CH2CH2CH3 600C, 10 atm + 4H2 + NaNO2 + HCl
0 – 5C C2 H5OH
+ N2 + CH3CHO
n – Hexane
CH3 N 2Cl

Pt-Al2O3 H3PO2 + H2O;Cu+

CH 3(CH 2)5CH3 500C
+ 4H2 or C 2H5OH/
or Na 2SnO 2/OH
Heptane
Touene vii) BENZENE PREPARATION FROM
(octane no = 0)
(Octane No. = 1040 GRIGNARD REAGENT
iv) DEHYDROGENATION OF  When bromo benzene is reacted with Mg in
presence of dry ether phenyl magnesium bromide
CYCLO ALKANE is formed which on hydrolysis benzene is formed
 When cyclohexane is heated with Pt or Se Br Mg B r
benzene formed.
 +M g Et h e r H 2O

Metal Oxide
H2C = CH – CH = CH2 + CH2 = CH2 600C - 700C – 2H2 viii) FROM CHLOROBENZENE
Butadiene Ethylene Cl

Cyclohexene Benzene Ni-Al alloy

+ 2[H] NaOH + HCl
v) REDUCTION OF PHENOL
Chlorobenzene MgX
 Distillation of phenol in the presence of zinc dust
gives benzene. Mg H2O/H +
Ether
OH

Zn-dust ix) DESULPHONATION

 Hydrolysis of benzene sulphonic acid with super
heated steam gives benzene.
Phenol Benzene SO3H
vi) FROM BENZENE DIZONIUM SALT
 When aniline is reacted eith nitrous acid at 150-200C
+ H2O (Steam) + H2SO4
00 to 50 C benzene dizonium chlorode is formed,
which on reduction with H 3 PO2 or ethyl alchohol
Benzene sulphonic acid
benzene is formed.
x) DECARBONYLATION
NH2 N2Cl
CHO
273-283
+ HNO2 + HCl + 2H2O
(Ph3P)3RhCl
Decarbonylation
Aniline 2[H]
H3PO2

Benzaldehyde
+ N2 + HCl + H3PO3 W.E-3: How would you covert the following
compounds into benzene ?
Benzene i) Hexane ii) Ethene

Narayana CO Programme CO Spark IIT - JEE 253

 BENZENE CHEMISTRY
Sol: i) n-hexane 
aromatisation
 Benzene GENERAL MECHANISM OF
Br2
ii) Ethene  CH 2  Br   CH 2  Br  ELECTROPHILIC AROMATIC -
SUBSTITUTION REACTIONS OF
Alc.KOH
 BENZENE - KINETIC ANALYSIS WITH
Ethyne NaNH 2
 vinyl bromide ENERGY PROFILE DIAGRAM
 All electrophilic substitution reactions follow
 Trimerization similar mechanism. The reaction takes place in
benzene
three steps.
FROM COAL TAR
Benzene on destructive distillation gives coal tar (1) Generation of electrophile
which on fractional distillation gives the following (1) Nu – E  Nu + E
components
S.No. Fraction Temperature Range % age Chief Constitutents
1. Light oil or Crude naphtha upto 170° 7-8 Benzene, Toluene, Xylene, etc.
2. Middle oil or Carbolic oil 170°-230° 8-10 Phenol, napthalene
3. Heavy oil or Creosote oil 230°-270° 16-20 Anthracene, Phenamthrene
4. Green oil or Anthracene oil 270°-360° 16-20 Anthracene, Phenamthrene
5. Pitch Residue 50-60 90-95% Carbon
PROPERTIES OF BENZENE
(2) Formation of carbocation
i) PHYSICAL PROPERTIES
E
 Aromatic hydrocarbons are generally colourless
liquids or solids with characteristic aroma.  
 Benzene is insoluble in water but soluble in organic +E Electrophile +H
solvents. Benzene and other aromat ic
hydrocarbons are highly inflammable and burn (2) + E 
slow step
E 
r . d .s

with a sooty flame
 B.P. of benzene is 800C  - complex
ii) CHEMICAL PROPERTIES OF BENZENE
(EAS)
H E H E H E
 Benzene and its derivatives mainly undergo

electrophilic substitution reactions. However, 

under special conditions, they also undergo 

addition reactions.
 - complex
Benzene preferably undergoes electrophilic
The carbocation formed in the above step is
substitution. But it gives three types of reactions
stabilised due to resonance.
they are
The reaction intermediate is areniumion or W
1. Electrophilic substitutions reaction wheeland intermediate.
2. Adition reaction (3) Removal of Proton
3. Oxidation reactions  In the last step, the carbocation loses a proton

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 CHEMISTRY BENZENE
from sp3 hybridised carbon to regain its aromatic  Other nitrating agents can also be used depending
character. upon nature of reactant.
(3) H E E (i) Conc.HNO3 , (ii) HNO3 + CH3COOH or
(CH3CO)2O, (iii) N2O5/CCl4,
  (iv) Acyl nitrate / ester
+H  The role of H2SO4 in the nitration mixture is to
eliminate water.
ENERGY LEVEL DIAGRAM FOR EAS
 A more detailed picture of the arenium ion  In nitration mixture HNO3 acts as base and
mechanism may be presented by its energy profile H 2 SO4 acts as acid.
diagram Note: In nitration mixture the total no.of ions = 4
H E....Nu  On heating the reaction mixture to about
E H....Nu
90  100C , m-dinitro benzene is obtained
NO2
Energy

conc.HNO3 + H2SO4
+ H2O
H E 90 - 100ºC

NO2
m - dinitro benzene
H
ii) HALOGENATION
 Electrophile is halonium ion (X+)
E
+ E – N  Order of reactivity of halogens is F2> Cl2>Br2>I2
+ H – N
 Order of reactivity of benzene is
C6H6  C6D6  C6T6
Reaction Co -ordinate  Chlorination and bromination may be carried out
Reacting coordinate(progress of the reaction) by X2/halogen carrier (Lewis acid, Fe-dust, I2
i) NITRATION etc.), HOCl or HOBr, Br2/(CH3COO)3Ti, Cl2O/
 Benzene when heated with a mixture of (1 : 1 by H2SO4, N-chloro or N-bromosuccinamide.
volume) concentrat ed nitric acid and Cl
concentrated sulphuric acid (nitration mixture)
below 600 C gives nitrobenzene. Anyd . Fecl
+ Cl – Cl   3
+ HCl
NO2
Mechanism
at 57 C
Con HNO3  Con H 2 SO4 ( or )
Step-1:


N2 O5  Acetic anhydride
( or ) Cl – Cl + FeCl3 FeCl4 + Cl
N2 O5 / 
Step-2 & st ep-3 are same as previous

mechanism.
H  O  NO2  H  HSO4  H  O  NO2  SO4 Iodination
|
Base Acid  Iodine reacts very slowly and iodination is carried
H
out by I2/oxidising agent (HNO3, HIO3, etc.), I2/
Cu may also be used
NO2  H 2O I
 
H 2O  H 2SO4  H 3O  HSO 4 Nitroniumion
HNO3
+ I2 + HI
  

HNO3  2 H2 SO4  NO2  2 HSO4  H 3O
Isotopic effect present

Narayana CO Programme CO Spark IIT - JEE 255

 BENZENE CHEMISTRY

In sulphonation, the energy barriers on either side

of carbocation are roughly the same height

therefore some carbocations go on to product,
some revert to starting material. Hence, there is
X
primary kinetic isotopic effect and reversibility.
 HOX iv) FRIEDEL CRAFT’S REACTIONS
a) FRIEDELCRAFT’S ALKYLATION
Note: When F2 gas which is diluted with inert gas is Benzene reacts with alkylhalide in presence of
reacted with benzene fluorobenzene is formed anhydrous AlCl3 and gives alkyl benzene. The
iii) SULPHONATION reaction is known as Friedel Craft’s alkylation
 Benzene undergoes sulphonation with the reaction.
following reagents
SO3H

Conc .H 2 SO4 ( or ) fu min g H 2 SO4


Chloro Sulphonic acid  CCl4 ( or )

SO3 in any organic osolvent ( or )
H 2 SO4  H 3 PO 4
H 2 SO4  H3 BO3

 The attacking electrophile is SO3 (from fuming

sulphuric acid i.e., H 2 SO4  SO3 )

Note: SO3 is neutral electrophile

Mechanism :
 SO3  HSO4  H 3O 
2H 2 SO4 
H
ArH + SO3   Ar
K1 K2

K-1 
  ArH + SO–3 + H
–
SO 3
Mechanism:

H SO3– –
R  X  AlX 3  R   AlX 4
SO3 H

Rearrangement possible
Energy

–
H SO3

CH(CH3)2
H
SO3H Anhy.AlCl3
+ SO3 + CH3CH = CH2

Cumene
Reaction Co -ordinate (Isopropyl benzene)

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 CHEMISTRY BENZENE
CH2CH3 CH = CH2 b) FRIEDEL - CRAFT’SACYLATION
 The reaction of benzene with an acyl halide (or)
CH 2 = CH2 Fe2O 3/Cr 2O 3
+ H2 acid anhydride in presence of Lewis acid as
AlCl3 650 C
catalyst to give acyl benzene is known as Friedel
Benzene Ethylbenzene Styrene - Craft’s acylation.
 Reactivity order R  F  R  Cl  R  Br  R  I
 Attacking electrophile is R+(Rearragement is
possible)
 Alkylating agents are (i) RX/Lewis acid
(ii) alkene/protonic acid (iii) ROH/H+
 Two types of catalyst are used:
a) Lewis acids : Anhydrous AlCl3, AlBr3, BF3 .
b) Protonic acids : H2SO4, HF etc. 
 Electrophile is acylium cation (R C O)
 With higher alkyl halides, the product is  Acylating agents: (i) RCOX/Lewis acid
rearranged due to formation of more stable (ii) RCOOH or (RCO)2O or
carbocation. CH2 = C = O/Lewis acid
 No rearrangement takes place
LIMITATIONS OFFIREDEL CRAFTS AND
ADVANTAGES OFACYLATION OVER ALKYLATION
 Reaction is not possible if deactivating groups like
-CHO, -NO2, -COCH3 etc. are attached to
aromatic ring because R  is weak electrophile.
 Aniline does not undergo Friedal-Craft’s
alkylation as the Lewis acid catalyst Co-ordinates
with amino group there by making it a strongly
deactivating group.
Con H2SO4  With (CH3)3C – COCl/AlCl3 alkylation takes
place but not acylation. Because less stable

(CH3 )3 C  CO decomposes to give more stable
Cl 
[ (CH3 ) 3 C ].
X
Anhyd. AlCl3

Cl  CH2 = CH – X No Fridel Craft

Anhyd. AlCl3 CH  C – X
at very low Temp” R
W.E-4: How will you synthesize
CH3
Anlydrous
2 + CH2Cl2 AlCl3 CH2
from benzene?

Narayana CO Programme CO Spark IIT - JEE 257

 BENZENE CHEMISTRY
ORIENTATION OF ELECTROPHILE IN
Hint:
O
MONO SUBSTITUTED BENZENE
 When a group is attached to benzene ring it
CH3
H3C
produces two effects
112. + O
AlCl3 Zn(Hg)/HCl
a) Activity effects b) Directing effects
CH3 (Clemmensen reduction)
Cl
GATTERMANN- REACTION Effect of rate
..
Substituent Effect on orientation

CH = NH CHO – .NH
. 2 (amino)
– .NHR (alkylamino)
Very strongly activating . Ortho, para-directing
– NR2 (dialkylamino)
..
– .OH
. (hydroxyl)
ZnCl 2 H 2O
+ HCN + HCl Boil
+ NH3 O
..
– NHCR (acylamino)
Benzene Aryl immine Benzaldehyde Strongly activating
..
Ortho, para-directing
– .OR
. (alkoxy)
GATTERMANN-KOCH REACTION O
..
CHO – OCR (acyloxy)
–R (alkyl)
Activating – Ar (aryl) Ortho, para-directing
– CH = CR2 (alkenly)
AlCl3,CuCl
+ CO + HCl Standard of comparison –H (hydrogen)
–X
(X = F, Cl, Br, I) (halogen)
– CH2X (halomethyl)
Benzaldehyde O
Deactivating Ortho, para-directing
..
Note: Phenols do not undergo Gattermann-Koch – N = O, – .S. – CH3

Reaction. – CH = CH – COOH
– CH = CH – CHO
Mechanism O
(formyl)
 – CH
AlCl3 + HCl  AlCl4 + H O
(acyl)
+  – CR
CO + H  H – C  O O
(carboxylic acid)
– COH
CHO Strongly deactivating
O
Meta-directing
(ester)
– COR
AlC l  O
+ HCl + AlCl3  4

– CCl
(acyl chloride)

–CN (cyano)
– SO3H (sulfonic acid)
CHLOROMETHYLATION
– CF3 (trif luoromethyl)
Summary of Electrophile Substution reactions of Benzene – NO2 (nitro)
Very strongly deactivating + Meta-directing
– NR3
Source of +
– NH 3
Name of the reaction Electrophile Product
Electrophile
+
Chlorination of benzene Cl (chloronium ion) Cl2 + AlCl3 (or) FeCl3 Ph – Cl  On the basis of activity effects, groups may be
divided into two types
Bromination of benzene Br+ (bromonium ion) Br2 + AlBr3 (or) FeBr3 Ph – Br
 On the basis of directing properties groups may
Alkylation of benzene +
R (Alkyl carbocation) RCl + AlCl3 Ph – R be of two types:
Acylation of benzene +
R – C = O (acylium ion) RCOCl + AlCl3 Ph.COR Ortho, Para - Directing Groups:
O
-R, -OH, -OR, -SH, -NH2, -SR, -NHR, -NR2, -
+
CH –C =O
Benzolyation of benzene 6 5 Ph.COPh CH 2 R, -C 6 H 5 , -X, -CH 2 OH, -CH 2 Cl,
(benzoyl cation) C6H5 – C – Cl + AlCl3
Benzoylchloride -CH 2 NH 2 , -CH 2 CN, -CH 2 COOH,
HNO3 + H2SO4
-CH = CH – COOH, -CH = CH2
Nitrotion of benzene +
NO2 (nitronium ion) Ph – NO2  These groups release electrons to the benzene
Nitrorating mixure ring makes the benzene ring more susceptible to
H2SO4 + SO3
the attack of electrophiles.
Sulphonation of benzene SO3 (sulphur trioxide) Ph.SO3H  Hence these groups are called ortho and para
Oleum
directing and ring activating groups

258 CO Spark IIT - JEE Narayana CO Programme

 CHEMISTRY BENZENE
CH3 CH3 CH3 CH3  In the ortho attack of electrophile
NO2 :NH2 :NH2 :NH2
HNO3
+ + E E
H2SO4 E
H H
59% NO2
NO2
37% E H

S S :NH2 NH2
S E E
Reaction H H
is faster
+ E 
Relatively stable
+
E H E H  Greater the number of possible canonical
structures greater will be the dispersal of charge
Transition state Arenium ion and greater will be the stability of arenium ion.
stabilised stabilesed  In ortho or para attack of electrophile, four
resonance forms are possible while in the attack
S = electron releasing group of electrophile at meta position, only three
 These groups increase electron density canonical forms are possible.
specifically at ortho and para positions. The  Hence, ortho, para directing group stabilises the
incoming electrophile specifically attacks at ortho ring to greater extent. Ortho and para positions
and para positions. Hence they are called ortho get more electron density through resonance.
and para directing groups.  Presence of o- and p - directing groups (activating
groups) facilitate nitration even with dilute HNO3.
In the para attack of electrophile:
OH OH OH
.. NH .. NH .. NH NO2
2 2 2 dil.HNO3
+
+H2SO4

 NO2
E

 Presence of m - directing groups (deactivating
E H E H
 groups) slow down nitration e.g. higher
NH2 ..NH2 .. NH2 temperatures are required to get di nitro and tri
nitro substituted benzenes.
Meta Directing Groups:
 NO 2 , -SO 3 H, -SOCl, -COR, -COCOOH,
E H   
-CX3,  N H3 ,  N HR 2 ,  N R 3 etc.
Relatively stable  These groups withdraw electrons particularly
from ortho and para positions thereby meta
 In the meta attack of electrophile
position is relatively more electron dense. Hence
these groups are called meta directing and ring
:NH2 :NH2 :NH2 :NH2
deactivating groups.
NO2 NO2 NO2 NO2
NO2
E E E HNO3
+
E +
H H H H2SO4
NO2
Relatively less stable NO2

Narayana CO Programme CO Spark IIT - JEE 259

 BENZENE CHEMISTRY
 Let ‘S’ be an electron withdrawing group. out of the ortho and para-positions, the new group
S S S entersp-position preferably with respect more
Reaction powerful group.
is slower
+E For example, in o chlorophinol, since- OH group
is more powerful than -Cl, the third group entetrs
E H E H the position para to -OH as indicated by arrow.
Transition state Arenium ion
destabilised destabilised NH2
-- - - - - -
O O O O O O O O
+ + + +
N N N N
+ +
Cl
+ other example is
 The resulting resonance hybrid, now possessing
positive charge in the ortho and para positions OH
repels approaching electrophiles increasing the
relative success of attack in the meta position. Cl
 So EWG act as meta directing group.
Inductive and resonance effects in the
ortho para orientation :
In case,the p-position is blocked , the third group
 Groups like halogen, -NO etc., which deactivate enters the position ortho to more powerful group.
by –I effect but activates by resonance. But the For example , in entrant is directed to ortho po-
overall electron density increases at ortho and sition as indicate by arrow because the p -posi-
para positions of the ring due to resonance. The tion being blocked.
electrophile attacks at these positions giving rise
to ortho and para disubstituted compounds. NH2

Cl Cl Cl
NO2
Nitration
+
Cl
NO2
other example is
ORIENTATION OF ELECTROPHILE IN
DI /POLY SUBSTITUTED BENZENE
CH3
1. The poisition occupied by a third substitu e n t
group enerting the benzene ring is mainly decided
by the nature of two groups already present on
the bezene ring.
(i) When the both gorups belong to class I (o-p- NH2
directing), the directive influence of each group (ii) When both the groups belong the class II (meta
is in the following order : directing) the third group is accmmondated on

O  NR2  NH 2  OH  OMe, benzene ring with difficulty. The directive
influeneceof each group is in the following order:
NHCOCH 3  CH 3  X 

 X   F  Cl   Br   I  Me3 N  NO2  CN  SO3H  CHO  COMe  COOH

The new entrant occupies meta position with re-
260 CO Spark IIT - JEE Narayana CO Programme
 CHEMISTRY BENZENE
spect to more powerful group W.E.-5:What happens when p-xylene is treated
For example, in nitrobenzaldyhyde, the new group with concentrated sulphuric acid and the
is directed to position shown by arrow. resultant product is fused with KOH and
CHO finally dilute acid is added?
Sol
OH
ii) fused KOH
NO2 ii) H3O

other example is
NO2

CH3

NO2
iii) When the two groups exert diffirent direc- W.E.-6: conc.HNO3 – conc.H2SO4
In the
tive influences the group belonging to class I
takes precedence. In case, the influences of two NO2
groups reinforce each other, the third group en- above reaction which product is most likely
ters alomost entirely in one position. to be formed?
CH
Examples are given below to examplain the above 3

ON
point. 2

CH3 CH3
Sol:
NO2
W.E-7: Complete the following reactions:
P -Nitrotolvene a) 4-bromo-2-methylphenol treated with 2-
NO2 NO2 methylpropene and sulphuric acid.
p-nitrotolvene b) p-cresol treated with propanoyl chloride
(position ortho to CH 3 and meta to  NO2 ) and aluminium chloride.
Cl c) 2,5-dichlorophenol reacts with chlorine in
NO2 acetic acid.
CH3 Sol:
NO2 (a) OH OH
smallerquantity CH3
H3C
CH3 CH3 CH3
Cl H2SO4
o-nitrochlorobenzene NO2 + H3C H3C
CH2

Largerquantity
Br Br
(b) OH OH O
CH3

AlCl3
+ H3 C
NO2 CH3
O
CH3
CH3
CH3 Cl CH3
Cl Cl
NO2
NO2 OH OH
m-nitrotoluene +2Cl2
CH3 CH3COOH
Cl Cl

NO2 Cl Cl

Narayana CO Programme CO Spark IIT - JEE 261

 BENZENE CHEMISTRY

Ipso substitution: CHMe2 NO2 CHMe2

NO2
In addition to O , m  and p-attack on C6 H 5Y HNO3 / H2SO4
+
there is, also the possibility of attack by an
electrophile on the ring carbon atom to which the
substituent Y is already attached: CHMe2 CHMe2 CHMe2
Y E  Group other than alkyl may also be displaced
E Y
during nitration reactions.
E –Y e.g. nitrodebromination:
–E Br NO2 Br
The net result, would thus be displacement of Y 
by E  . Such an overall reaction is referred to as HNO3 +
ipso substitution. Ac2O
A number of such reaction are known in which NO2
the attacking electrophile is H  : O Me O Me O Me
 An Me3C substituent may be displaced  Analogous nitrodechlorination is not observed,
particularly readily in this way (protodealkylation), however, owing to the greater resistance to for
but we have already seen similar displacement of mation of Cl  , compared with Br  .
a more familiar subst ituent SO3H Br
(protodesulphonylation), in the reversal of
sulphonation: Br2
Me3C H

H  OMe OMe
 
(HClO 4 )

 Ipso attack at a substituted position appears to
be promoted by the presence of other
OH OH substituents that can exert a directing (activating)
(protodealkylation)
effect towards this position.
 Protodealkytion possible when carbocation is
ADDITION REACTIONS
stable.
SO3H H ADDITION OF X2 IN UV LIGHT
 Benzene undergoes addition reactions under
 special conditions.
H Addition of Chlorine
+ H2SO4
H2O  Benzene reacts with chlorine in presence of
(protodesulphonylation) sunlight to give benzene hexachloride (BHC) or
 A factor expected to promote ipso substitution hexachlorocyclohexane or Gammaxene or 666
would be ease of formation of the potential leaving or Lindane.
group, Y  . This is borne out by known  Benzene reacts with chlorine or bromine in
presence of sunlight or ultraviolet light and in
displacement of secondary and tertiary alkyl
absence of halogen carrier (such as
substituents, reflecting the relative stability, and
ease of formation of the relevant carbocations, only FeCl3 & AlCl3 etc) to produce crystalline
R  ; e.g. in the nitration (nitrodealkylation): hexachlorides and hexa bromides respectively.

262 CO Spark IIT - JEE Narayana CO Programme

 CHEMISTRY BENZENE
Cl Step-2:
Cl Cl The Anion radical is a strong base and abstract a
+ 3Cl2
proton from Methanol.
 
Cl Cl
Cl + H – O – CH3
Benzene hexachloride (BHC)
 - isomer is Gamaxene (or) 666 (or) lindane
 BHC is a powerful insecticide H
Step-3:
SIDE CHAIN HALOGENATION - NBS, NCS, The cyclohexadienyl radical produced in step-2
Cl2 LIGHT SO2Cl2 is converted to an anion by electron transfer from
CH3 CH2Br Na and proton transfered from Methanol.
H
NBS
 Na  Na+ + le– CH3 – O – H

Free radical substitution

Note : Free radical substitution
 H H H
Examples:
CH3 CH3
COOH COOH
NBS(Ag)

Na(or)Li/

Liq.NH3 (or)R-OH

Br
E substitution
Na/Liq.NH
Note : E  - substitution  3
C H OH 
2 5
REDUCTION OF BENZENE
(HYDROGENATION OF BENZENE) OCH3
 At high temperature and pressure, in presence of OCH3
finely divided nickel, benzene undergoes Li
liq.NH3 
hydrogenation to give cyclohexane.
Ni / 150ºC Methoxy benzene 1-Methoy-
+ 3H2 25 atm (anisole) 1,4-cyclohexadiene (84%)
Cyclohexane
 In presence of Pt, reaction occurs at room SIDE CHAIN OXIDATION - POWERFUL
temperature OXIDISING AGENT
Oxidation with KMnO4
Birch Reduction R COOH
Li or Na/
Liq NH3 or CH3-OH 4

KMnO

Mechanism
Step-1: Benzoic acid
An electron is transfered from Sodium to  - CH3
system of aromatic ring.
CH3 C CH3

KMnO
4
  no reaction at ordinary
conditions

Narayana CO Programme CO Spark IIT - JEE 263

 BENZENE CHEMISTRY

Note : Alkyl benzenes with atleast one NO2 D

Conc.HNO3 D+
H2O + H2SO4

D2O + H+
benzylic hydrogen on oxidation with KMnO4
give benzoic acids.
O SO3H N=O
Conc.H2SO4 NaNO2
   + H2O
H2O + SO3 HCl

V2O5

 O + CO
Cl N=N–Ar
ArN 2 X 
O HCl +
Cl2
FeCl3

CuplingReaction + HX
W.E-8:Compounds (A) and (B) are isomers
having the formula C8H10. On oxidation (A)
gives benzoic acid while (B) gives phthalic R CHO
acid which forms an anhydride (C) on heating. HCl +
 RCl.AlCl 3
(Fredal-Craft's alkylation)
 CO+HCl/AlCl3
(GatternmannKochsynthesis)


Identify (A), (B) and (C).

Hint: O
CHO
C
(A) is CH3 RCOCl.AlCl3 (or)Acidanhydrate.AlCl 3


(Friedal -Craft's acylation)
 HCN +HCl
AlCl3  H3O + + H+
HCl + R (Gatternmannsynthesis)

OZONOLYSIS OF BENZENE AND

DERIVATIVES
 One mole of benzene reacts with three moles of
ozone to give a triozonide, which on hydrolysis
in presence of zinc gives three moles of glyoxal.

where (B) is + 3O3 C6H6(O3)3

Benzene triozonide
H2O / Zn

CHO – CHO + 3H2O + ZnO

glyoxal
(3 moles)
 Zn dust destroys H2O2 which may otherwise
O oxidise glyoxal to oxalic acid.
HO O
CH3 O O CH3
O
CH3 O O O O
[O] OH  3O3
– H2O
Zn/H2O
CH3 – C – C – H + 2H – C – C – H
methyl glyoxal glyxal
O CH 3 CH3 CH 3
CH3 CH3 CH3
i) 3O3
CH3 OH ii) Zn/H2O
[O]

2) Combustion:
O O O
15 CHO

C6 H 6  O2   6CO2  3H 2O 3 + 2CH3 – C – CHO + CH3 – C – C – CH3
2 CHO

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 CHEMISTRY BENZENE
 Above addition reactions of benzene prove the TOLUENE
presence of three double bonds in benzene but Preparation methods of Toluene:
they are different from aliphatic double bonds in
CH3
following reactions:
i) Benzene does not decolorise Br2/H2O or cold AlCl3
1) + CH3I
alk.KMnO4
ii) Benzene does not give addition reaction with
HX or HOX Br CH3
W.E-9: What are the ozonolysis products of ortho
dry
2) + 2Na + CH3Br + 2NaBr
xylene ? ether
Bromomethane
Sol : 1,2-Dimethylbenzene (o-Xylene) on ozonolysis Bromobenzene
gives glyoxal, methyl glyoxal and dimethyl glyoxal 3)
in 3 : 2 : 1 molar ratio. CH3
It proves the existance of two resonance
structures for benzene and its derivatives. Al2O3/Cr2O 3
CH3CH2CH2CH2CH2CH2CH3 500 C, High pressure
Carcinogenicity and Toxicity n-heptane
MgI CH3

dry
+ CH3I re?ux
+ MgI2
H3 C Phenyl magnetism
iodide
1,2-Benzanthracene 3-Methylchloanthrene
CH3 CH3

CaO
+ NaOH 

Toluene
1,2-Benzpyrene COONa
Sodium salt of
CH3 par toluic acid
Chemical methods of Toluene:
CH3 COOH
CH3
9,10-Dimethyl-1,2-benzanthracene –
KMnO4/OH /

Uses of Benzene :
Benzoic Acid
 It is used as solvent for fats and resins.
CH3 CH2OH
 It is used in drycleaning.
 It is used in the synthesis of phenol, styrene, SeO 2
aniline, insecticides like BHC.
 It is used as a motor fuel. Benzylalcohol

Narayana CO Programme CO Spark IIT - JEE 265

 BENZENE CHEMISTRY
W.E.-11:What is the major product obtained by
CH3 COOH
nitration of m-xylene?
Sol. In m-xylene, both methyl groups are o-, p-
V 2O5
+ 3O2 300C 2 + 2H2O directing. The major product is 1-nitro-2,4-
dimethyl benzene.
Vapour Air
CH3 CH3
CH3 CH3
Nitration

H2/Ni/ 
CH3 CH3
NO2

CH3 CH3 CH3 W.E.-12.Predict the major product of

chlorination of m-dinitrobenzene.
(i) Na/NH3(l)
(ii) C2H5OH
+ Sol. In m-dinitrobenzene, both nitro groups are
Major Minor
m-directing. Further substitution occurs at meta
position to each –NO2 group. The major product
CH3 CH3 CH3 is 1-Chloro-3,5-dintro benzene.
NO2
HNO 3/ NO2 NO2
+
o-nitrotoluene Chlorination
NO2
p-nitrotoluene NO2 NO2
Cl
 Benzene and several polynuclear hydrocarbons
like 1,2-benzanthracene, 3-methyl cholanthrene, W.E.-13:. Write the major product of the
1,2-benzpyrene , 1,2,5,6- Dibenzanthracene are following reaction.
toxic and said to be carcinogenic
 Most of these are formed due to incomplete
combusion of tobacco, coal, petroleum etc. Cl2
 They undergo various biochemical changes in FeCl3

human body and finally damage DNA to cause
cancer. Sol. In 2-nitrotoulene, methyl group and nitro group
W.E.-10: What product is obtained when isobutyl direct the electrophile into para position of the
chloride reacts with benzene in presence of methyl group which is meta to nitro group.
AlCl 3 ?
Sol. The initially formed carbocation rearranges to a Hence the major product of the reaction is 4-
more stable tertiary carbocation as shown. chloro-1-methyl-2-nitrobenzene.
CH3
C CH3
+ Cl 2
+ (CH3)3C CH3 
FeCl3


The final product of the reaction is tert.butyl

benzene.
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 CHEMISTRY BENZENE
W.E.-14 . How acetic acid can be converted to The increased reactivity is a result of resonance
benzene? which pushes the electrons from the N-atom into
the ring making the c-atoms of pyrrole ring more
NaOH(aq) Soda lime electron rich than in case of benzene. In fact
Sol. CH3COOH CH3COONa CH4 pyrrole resembles most reactive benzene
Cl2 Na/dry ether Cl2 derivatives (phenols and amines)
CH3Cl Wurtz reaction C2H6 C2H5Cl
Consequently, there are some modifications in
alc.KOH
CH2= CH2
Br2
CH2Br CH2Br
alc.KOH usual electrophilic reagents, for instance,
sulphonating and nitrating reagents have been
NaNH2 Red hot iron tube modified to avoid the use of strong acids(induce
CH2= CHBr CH CH C6H6
873 K polymerization). Also reaction with halogens
ADITIONAL MATTER requires no Lewis acid.
Electrophilic substitution in Reactivity of electrophilic substitution
heterocyclic compounds
In comparison to benzene pyrrole is more is more > >
reactive towerds electrophilic aromatic N N
substitution thus the substitution is easier and |
milder reagents can be used. H
Regio selectivity of electrophile substitution

 Thiophene is the most aromatic in character and undergoes the slowest reaction.
 Pyrrole and furan react under very mild conditions.
  -substitution favoured over  -substitution more resonance forms for intemediate so the charge is less
localised (also applies to the transition state)
 Some  -substitution usually observed - depends on X and substituents.
NO2
Ac ONO
2
  +

.X. X
.. NO2 X
..
X = NH 4 : 1 X=O 6 : 1
 Order of Aromaticity  Thiophene > Pyrrole > furan
 Order of reactivity  Pyrrole > furan > thiophene  benzene
 Furan can give addition as well as substitution products when reacted with E 
 Thiophene can give electrophilic substitution and not addition.

Narayana CO Programme CO Spark IIT - JEE 267