STEM

NaOOC
PREPARATIONS 1) Halogenation PROPERTIES

OHC
+

CaO
X2 / AlX3

HO3S

NaOH

HO
R.T

HO3S
Zn-dust
2)Sulphonation
HO3S

HO3S


200-2450C
CO+HCl /AlCl
3
280-3000C

HO3S
SO3H

Velammal IIT & Medical Foundation

dil.HCl under P

H2N

H2SO4+SO3
Red Hot Cu tubes Sn/HCl
3

CH
CH
O2N

< 600C
SO3H O2N

3)Nitration
Conc.HNO +H SO > 600C
3 2

O
4
NO2

O
O3
R

O
Ozonolysis Friedel Craft alkylation
3
H3C

Zn/H2O

O
R-X + AlX

O O

CHO
CHO
3

O
Glyoxal
CH

O
Friedel Craft alkylation
Benzene triozonide
CH3

Alkylation

O
CH3CH2CH Cl + AlCl Rearranged Product
2 3

O
CH3 CH=CH / H+
2

CH3CH2CH OH + H+
2

O
V2O5 4500C

Friedel Craft acylation

COR

O
R-COX + AlX
Maleic anhydride 3

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HYDROCARBONS
STEM HYDROCARBONS

AROMATIC COMPOUNDS
Greek word ‘aroma’ means pleasant smelling.
Benzene was considered as parent ‘Aromatic’ compound.
But now, the name is applied to all the ring systems whether or not having benzene ring, possessing
following characteristics.
I. Cyclic Planar molecules with conjugated  bonds.
II. Complete delocalisation of the  electrons in the ring which lowers the electronic energy.
III. Presence of (4n+2) electrons in the ring where n is an integer (n=0,1,2,3....)
HUCKEL RULE.

It has 6  electrons It has 10  electrons

Benzene Naphthalene
4n+2=6 and here n=1. 4n + 2 = 10 and hence n = 2.
It has 14  electrons It has 6  electrons

Anthracene Cyclopentadienyl anion

4n + 2 = 14 and hence n=3 4n + 2 = 6 and hence n=1.

It has 6  electrons It has 2  electrons

Cycloheptatrienyl cation Cyclopropenyl cation

4n + 2 = 6 and hence n=1. 4n + 2 = 2 and hence n=0.

Aromatic compounds are classified as follows

I. Carbocyclic(Aromatic Hydrocarbons)
II. Heterocyclic : One or more carbons in the ring are replaced with Heteroatoms like
N,O,S.
N N
N
N
N N N N
H
H H N N N N
Pyrrole Imidazole Pyrazole Pyridine Pyrazine Pyrimidine Pyridazine
O

O S O
Furan Thiophene Benzofuran Xanthene

AROMATIC HYDROCARBONS:
Aromatic hydrocarbons possess a higher percentage of carbon as compared to aliphatic hydrocarbons.
They burn with sooty flame.Most of Aromatic hydrocarbons were found to contain Benzene ring.
However, there are some of aromatic Hydrocarbons which do not contain a benzene ring but
instead contain other highly unsaturated ring.

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Hence aromatic hydrocarbons are classified as

I. Aromatic hydrocarbons containing benzene ring - Benzenoids ( Arenes)
General molecular formula Cn H 2 n 6 y . (n  6 and y is number of benzene rings).
a) Mono cyclic - Benzene
b) Polycylcic - i) Isolated polycylic
ii) Fused polycyclic

benzene naphthalene anthracene phenanthrene Pyrene

Fused Polycyclics

biphenyl Diphenyl methane Benzyne Phenalen-1-ide

Isolated polycyclics (Phenalene anion)
Pyrene

II. Aromatic hydrocarbons without benzene ring - Non Benzenoid

Cycloproenyl Cyclobutene Cyclopentadienyl Cycloheptatrienyl Cyclooctatetraene

carbocation di carbocation anion carbocation dianion

Azulene
[14] Annulene [18] Annulene
Annulenes
The name annulene has been proposed as a general name for monocyclic compounds that can be
represented by structures having alternating single and double bonds. The ring size of an annulene is
indicated by the number of pi electrons in brackets. Thus, benzene is [6] annulene and cyclooctatetraene
is [8] annulene, Huckel’s rule predicts that annulenes will be aromatic, provided their molecules have
(4n  2) electrons and have a planar carbon skeleton.
Solved Problem: Identify the aromatic, annulenes from the following examples
[14], [16], [18], [20], [22] and [24] annulenes.
Solution : Huckel’s rule predicts, the [14], [18] and [22] annulenes satisfy (4n + 2 when n = 3, 4, 5,
respectively) have been found to be aromatic.
Anti Aromatic:
Compounds satisfying following rules are referred as antiaromatic.
I. Cyclic Planar molecules with conjugated  bonds.
II. Complete delocalisation of the  electrons in the ring which increases the electronic energy.

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III. Presence of (4n) electrons in the ring where n is an integer (n=0,1,2,3....)

Some examples of anti aromatic compounds.
IV. Much more reactive than expected and even more reactive than acyclic analogues. Thus
decreasing stability is referred as antiaromaticity.

C yclopropenyl C ycloheptatrienyl
anion Cyclobutadiene C yclopentadienyl ion anion
Non-Aromatic:
Cyclic compounds having 4n or 4n+2 electron systems which lacks planarity.

(1Z,3Z,5Z,7Z)-cycloocta-1,3,5,7-tetrene
cyclodeca-1,3,5,7,9-pentene
All cis bonds - non aromatic
Should be anti aromatic
but change shape to avoid it.

H
H

cyclodeca-1,3,5,7,9-pentaene
(1Z,3Z,5Z,7Z)- Repulsion b/n two H make
cycloocta-1,3,5,7-tetraene it out of plane

Solved Problem : Identify the aromatic, annulenes from the following examples
[14], [16], [18], [20], [22] and [24] annulenes.
Solution : [16] annulene and the [24] annulene are anti aromatic.
4n = 16 pi electrons thus n = 4 (an integer).
4n = 24 pi electrons thus n = 6 (an integer).

STABILITY ORDER
AROATIC > CONJUGATED NON - AROMATIC >
NON-CONJUGATED COMPOUND >ANTI-AROMATIC

Homocyclic aromatic compounds or Arenes

Aromatic compounds containing atleast one benzene ring
General formula : C n H 2n  6 which include benzene and its homologues.
Nomenclature : The substituent name is placed as prefix or suffix to the word benzene

Cl CH3 OCH3 SO3H N2Cl

chlorobenzene Methyl benzene Methoxy benzene Benzene Benzene

(toluene) (anisole) Sulphuric acid diazonium chloride

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The dimethyl benzenes are xylenes

CH3 CH3
CH3
CH3

CH3
CH3
1,2-dimethyl benzene 1,3-dimethyl benzene 1,4-dimethyl benzene
(o-xylene) (m-xylene) (p-xylene)

When two substituents are present, their relative positions are indicated by the prefixes ortho, meta or
para(o-;m-;p). These prefixes are only for disubstitued compounds but, for more substituted compounds
numbers are given

Cl Cl NO2
Cl COOH

Cl Cl
Cl
1,2-dichlorobenzene 1,3-dichlorobenzene 1,4-dichlorobenzene 2-nitrobenzoic acid
(ortho dichlorobenzene) (m-dichlorobenzene) (para-dichlorobenzene) (o-nitrobenzoic acid)

Position of more than two substituents are always indicated by numbers

Br Br Cl
Br Br

Br Br O 2N NO2
1,2,3-tribromo 1,2,4-tribromo 1-chloro-2,4-dinitro
benzene benzene benzene
COOH CH2 -CH2 -CH2 -CH3 OH NO2

O2N NO2
3,5-dinitro benzoic acid butyl beneze Hydroxy benzene nitro benzene
(phenol) (oil of mirbane)
(The names written in brackets are common names which are frequently used.)
H3C C CH CH3 H3C C CH CH3 CH2-
(or) C6H5 (or) C6 H 5  CH 2 

2-phenyl-2-butene benzyl
C6 H 5  group is known as phenyl ,which is some times abbreviated as Ph or  .
Structure of Benzene : Benzene was isolated by Michael Faraday in1825.
1. The molecular formula of benzene, C6H6 , indicates a high degree of unsaturation.
2. This molecular formula did not account for its relationship to corresponding alkanes, alkenes and alkynes.
Since It
a) cannot decolourise Br2 water (or) alkaline KMnO4 (Test for unsaturation)
b) It can't undergo Polymerisation and oxidation under normal conditions.

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3. Due to its unique properties and unusual stability, it took several years to assign its structure.
4. Benzene was found to be a stable molecule and found to form a triozonide which indicates the presence
of three double bonds.
C6H6 + 3 O3 C6H6(O3)3
Benzene triozonide
5. Benzene was further found to produce one and only one monosubstituted derivative which indicated
that all the six carbon and six hydrogen atoms of benzene are identical.
C 6H 6 + X C 6H 5X
M on o substitu ted
B en zene
6. On the basis of this observation August Kekulé in 1865 proposed the following structure for benzene
having cyclic arrangement of six carbon atoms with alternate single and double bonds and one hydrogen
atom attached to each carbon atom.
H
C
H C C H

H C C H
C
H
7. The Kekulé structure indicates the possibility of two isomeric 1, 2-dibromobenzenes. In one of the
isomers, the bromine atoms are attached to the doubly bonded carbon atoms whereas in the other,
they are attached to the singly bonded carbons.
Br Br
Br Br

But, Benzene forms only one ortho substituted product. Hence kekule suggested that the pi bonds
will be oscillating and result both the structures.

K ekule stru ctures

8. Drawback: Fail to explain the unusual stability and preference to substitution than addition
reactions of benzene.
STABILITY OF BENZENE:
The stability and the structure of benzene have been explained on the basis of two modern theories.
I) Resonance or valence-bond theory II) Molecular orbital theory
Resonance theory
1. Resonance:
a) The phenomenon in which two or more structures can be written for a molecule but none of them
represents its actual structure is called resonance.
b) Various possible alternative structures are known as resonating structures or Canonical
structures.
c) In these structures only delocalization of electrons takes place.
d) During this delocalization some energy is released which is called resonance energy.

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e) Greater the resonance energy greater will be the stability.

f) More the number of resonating structures or canonical structures more will be the stability.
Benzene is believed to be a resonance hybrid of the following resonance or cannonical structures.
(1) and (2) structures (Kekule) are far more stable than the Dewar’s structures. Thus these two
kekule structures contribute more to resonance hybrid (80%) than the rest of the structures.

20% Benzene
80% Resonance Hybrid
Kekule's Structures Dewar's Structures

2. a) Since, the two Kekule’s structures are equivalent, the stability of the resulting resonance hybrid is
very high.
b) Due to resonance, each C-C bond in benzene has some double bond character confirmed
experimentally.
The bond length C-C (single bond as in ethane) is 1.54 Ao and
C=C (double bond as in ethene) is 1.34Ao.
o
C C (bond length in benzene) is 1.39 A ,
This indicates C-C bond length in benzene is in between single and double bond lengths.
3. Hydrogenation reactions of benzene also explain the stability of benzene.
Pt Pt
+ H2 + H2

Cyclohexene Cyclohexane 1,3-cyclohexadiene

; H 28.6k cal mol1 ; H  55.4k cal mol 1 (just double that of cyclo hexene)
If benzene was a hexatriene then
the energy to be liberated in hydrogenation is 3  28.6  85.8 k .cal.mole 1
but actually benzene liberates only 49.8 k cal mole-1. .
Benzene is stabilized compared to cyclohexatriene to the extent of 85.8  49.8  36 k .cal / mole .
For Benzene resonance energy is 36 K.cal/mole or 150.48 KJ/mole.
Orbital Model of Benzene
1. Benzene is hexagonal planar. All the six carbon atoms undergo sp 2 hybridisation.
2. Each carbon is surrounded by three sp 2 hybridized orbitals and one unhybridized ‘p’ orbital
with unpaired electron.
3. The six unhybridised ‘p’ orbitals form three delocalised  bonds by side wise overlapping
4. The total number of hybridised orbitals and pure orbitals are 18 & 12 i.e., in 3 : 2 ratio.
5. The total number of  and  bonds in benzene are 12 & 3 i.e., 4 : 1 ratio
6. The Bond angle is 1200, and the bond length is 1.39 Ao due to delocalisation of '  'electons(or) resonance
Benzene (Aromatic) Cyclo octatetraene (Nonaromatic)
Antibonding  orbitals Antibonding  orbitals
Nonbonding  orbital  Nonbonding  orbital 
Bonding  orbitals Bonding  orbitals
Energy levels Type of
Energy levels Type of
of MOs  orbital
of MOs  orbital

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Kekule structures represented in orbital form

or or

Orb ital rep resen tat ion of

K eku le B enzene stru ctures.

The six  electrons are thus delocalised and can move freely about the six carbon nuclei, instead
of any two as shown in Kekule structures. The delocalised  electron cloud is attracted more
strongly by the nuclei of the carbon atoms than the electron cloud localised between two carbon
atoms. Therefore, presence of delocalised  electrons in benzene makes it more stable than the
hypothetical cyclohexatriene.

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Some other formulae of benzene

a) Landen berg’s b) Claus - diagonal c) Dewar’s Parallel d) Arm strong and Bayer’s
formula formula formula centric formula

Preparation of Benzene
1. From Coal (Commercial Method)
a) Coal is subjected to destructive distillation at 10000 C -14000 C in the absence of air in iron retorts
it gives four products.
i) Coal gas ii) Coal tar iii) Ammonical liquor iv) Solid residue.
b) Coal tar is black viscous oily liquid and is rich in hydrocarbons and their derivatives.
c) Water is removed by heating it and then subjected to fractional distillation.
The various fractions obtained from coaltar are
i) Fractions collected upto 1700 C Light oil Benzene, Toluene, Xylene
ii) Fractions collected between 170  230 C 0 Middle oil Phenol,Naphthalene ,Pyridine
(or)Carbolic oil
iii) Fractions collected between 230  2700 C Heavy oil Cresol, Napthalene
(or)Cresote oil.
iv) Fraction collected between 270-4000 Anthracene oil Anthracene, Phenanthrene.
(or) green oil
v) The residue left in iron retorts Pitch - It is used in road making and in the
preparation of varnishes.
d) Light oil is treated with H2SO4 to remove basic impurities. The excess of H2SO4 and phenol are
removed by treating with NaOH . Finally it is washed with H 2O and subjected to fractional distillation.
e) The first fraction is collected upto 1100 C . The second fraction is collected upto 110  140 0 C  .
f ) The two fractions mixed and distilled. Benzene is collected between 80  810 C .
2. Laboratory Methods
a) Decarboxylation of benzoic acid
On heating sodium benzoate with soda lime gives benzene. It is a laboratory method of preparation.
C 6 H 5 COONa  NaOH  CaO
  C 6 H 6  Na 2 CO3
3. Reduction of Phenol
Distillation of phenol in the presence of zinc dust gives benzene.
OH

+ Zn  + ZnO

4. From Acetylene
On passing acetylene gas through red hot iron or copper tube, benzene is formed.
600o C
3C 2 H 2  
Cu
It can be catalysed by Al4C3 or carbon.

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5. Hydrolysis of Benzene Sulphonic Acid

Hydrolysis of benzene sulphonic acid with super heated steam gives benzene.
SO3H

+ H2O + H2SO4

6. From Chloro Benzene

Mg H 2O
C6 H 5Cl  
dry ether
 C6 H 5 MgCl   C6 H 6  Mg  OH  Cl 
7. Fom Aniline
NH2 N2Cl

+ HNO2 + HCl 273-283 + 2H2O

Aniline
2[H]
SnCl2/NaOH

+ N2 +HCl

Benzene
PHYSICAL PROPERTIES
Aromatic hydrocarbons are generally colourless liquids or solids with characteristic aroma.
Benzene is insoluble in water but soluble in organic solvents. Benzene and other aromatic hydrocarbons
are highly inflammable and burn with a sooty flame
B.P. of benzene is 80oC
CHEMICAL PROPERTIES
Benzene and its derivatives mainly undergo electrophilic substitution reactions. However, under special
conditions, they also undergo addition reactions.
ELECTROPHILIC AROMATIC SUBSTITUTION REACTIONS
1. Benzene contains three double bonds. Hence it is expected to undergo addition reactions. If it undergoes
addition reactions the product will be non-aromatic. To retain aromaticity it undergoes electrophilic
aromatic substitution reactions
2. An aromatic ring has negative charge cloud below and above its plane.Electrophiles being positively
charged or electron-deficient species are very prone to attack the negative charge cloud of the delocalized
e’s. Therefore, electrophilic reactions will occur on aromatic rings much readily.
3. An aromatic compound wants to preserve its aromatic character due to its stability and therefore it may
be reluctant to utilize its e’s.
4. Hence the electrophiles react with aromatic compounds not readily but slowly.
5. The most important type of reactions that the aromatic compounds undergo is the bimolecular electrophilic
substitutions which are designated as SE2 aromatic.
6. Formation of electrophile is followed by SE2 reaction.
Generation of electrophile:
Nitration:
a) The electrophile, nitronium ion is produced by transfer of proton from sulphuric acid to nitric
acid in the following manner :
H
H |
HO3SO H + H–O–NO2 H–O–NO2 + HSO4– H  O  NO2 H 2O  NO2
Protonated ; Nitronium ion
Nitric Acid Electrophile

In nitration mixture, H2SO4 behaves as an acid and HNO3 as a base.

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b) N2O5 in CCl4 when used, results in a spontaneous dissociation reaction.


N2 O5 NO2 + NO3
c) With concentrated HNO3 alone
2HNO3  NO2  NO3  H 2 O
Chlorination: Chloronium ion (Cl+) formed , acts as electrophile.
Cl2+ FeCl3   Cl+ + FeCl4–
Sulphonation: Electrophile is SO3
Conc. Sulphuric acid 2H2SO4  SO3 + H3O+ + HSO4–
Fuming sulphuric acid (oleium; H2S2O7 – sulphur trioxide in sulphuric acid)
Sulphur trioxide in an organic solvent (nitromethane, pyridine etc)
Chlorosulphonic acid in carbon tetrachloride
Aromatic sulphonation is a reversible reaction.
At low temperatures, the reaction is practically irreversible since the reverse reaction, known as
desulphonation reaction, is very slow.
Friedel Crafts alkylation: The electophile is R+ (Alkyl carbocation)
Alkyl halides by themselves are insufficiently electrophilic to react with benzene.
AlCl3 serves as a Lewis acid catalyst to enhance the electrophilicity of the alkylating agent.
The mechanism for the reaction starts with the formation of carbocation.
The carbocation then acts as an electrophile.
Some times carbocation rearrange to a more stable carbocation.
RCl  AlCl3  R  AlCl 4

Friedel Crafts acylation: The electrophile is R C O

RCOCl  AlCl3  R C O  AlCl 4 
 
CH 3 COCl  AlCl 3  CH 3 C O  Al Cl 4

 CH3CO2 O  AlCl3 
 CH C O  AlCl (CH COO)
3 3 3
7. Aromatic SE2 reactions are supposed to occur in two discrete steps:
Step I: The electrophile, E+, is attacked by the aromatic substrate laterally i.e., perpendicular to the
ring and forms a sigma-complex or Wheland complex (or cyclohexadienyl cation in the case
of benzene) in which a specific atom of the electrophile forms a covalent bond with a
specific C atom of the ring.
The involved sp2 hybrid C atom of the ring then assumes sp3 hybrid state.
The sigma complex formed is non aromatic and this step is highly endothermic.
The sigma complex is stabilised through resonance.
This step is rate determining step.
H
E E E E
slow


 E  
 +
H H H H H
Non-Aromatic H

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Step II: The -complex gives up a proton and gets converted into another aromatic compound,a
derivative of the aromatic substrate. The non aromatic intermediate sigma complex loses proton
and form aromatic product. This step is highly exothermic.
H
E E E E
+ E
H H H H H
H

Since the -complex consists of the electrophile and the substrate, the transition state of the
reaction involves each of them; and hence aromatic electrophilic substitution reactions are
usually bimolecular reactions.

E  E
 

H H
T.S. I T.S. II

The over-all reaction is


E E E
+ +
E   E H

H H H
T.S.I T.S.II

Since the T.S. of the rate-determining step of an aromatic SE2 reaction involves two species,
it is expected that the reaction will follow the second order kinetics.

T.S. I
T.S. II

 Complex

Reagent &
G Substrate Product

Progress of the reaction


The energy profile of an exothermic aromatic SE2 reaction without the formation of a
-complex
The evidences for the two step mechanism are:
a) Detection and isolation of -complexes: A large number of -complexes, as intermediates in
Ar. SE2 reaction, have been detected by n.m.r. spectroscopic study. Some of them have also
been isolated as -complex salts.
b) Primary kinetic isotope effect:
i) Displacement of an H (or D) atom of C6H6 (or C6D6) by a nitronium ion NO2+ is an aromatic
SE2 reaction.
ii) Experimentally it has been found that the rate of formation of C6H5NO2 from C6H6 is almost
equal to the rate of formation of C6D5NO2 from C6D6 under the same set of conditions.

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iii) If the C—H bond breaking step i.e., the step II of the Ar. SE2 reaction were a RDS, then
C6D5NO2 would have been formed more slowly than C6H5NO2. Since this does not happen,
the -complex formation step i.e., the first step is the rate determining step.
iv) It doubtless that the -electron cloud of an aromatic system invites an electrophile to react,
otherwise the electrophilic substitution reactions do not occur readily.
v) Rate of reaction may differ based on usage of
Strong electrophiles and electron-donating substituents which have +I, +R and /or
hyperconjugative effects, on aromatic rings which enhance the rate.
Weak electrophiles or electron-withdrawing substituents which have –I and/or –R, decrease
the rate of an Ar. SE2 reaction.
vi) The groups which increase the rates of Ar.SE2 reactions by donating electron to the ring are
called activating groups they activate the ring by +I, +R and hyperconjugative effects.
vii)–I and –R groups withdraw electrons from an aromatic ring and thereby slow down Ar. SE2
reactions and, therefore, they are called deactivating groups.
viii) Effect of substituents on rates of Ar. SE2 reactions (Standard of comparison is H atom)
Nature of group and examples Electrical effect
Activating
    
 +R effect predominates over the
  O,

 NR 2 ,  NR 2 ,  OH, 
  —I effect
    
 NHCOR,  OR,  O COR   O : does not have –I effect
    

—Ar Conjugative effect

—R +I and Hyper conjugative effect
Deactivating

–I-effect predominates over the
— X:
 +R-effect
—CX3, SR2+, NR 3+ —I-effect
—CHO,—COOH,—COCH3,
–I and —R-effects
—CN,—SO3H, —NO2
Ar. SE REACTIONS
1. Halogenation
a) Electrophile is halonium ion (X+)
b) Order of reactivity of halogens is F2 > Cl2 > Br2 > I2
X

A lX 3
+ X2 + HX

c) Fluorination is not carried out directly as F2 is highly reactive. Fluorination is carried out indirectly by
decomposition of benzene diazonium fluoroborate.

N2+BF4- F


 + BF3 + N2

Fluorobenzene

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d) Chlorination and bromination may be carried out by

X2/halogen carrier (Lewis acid, Fe-dust, P, I2 etc),
HOCl or HOBr, Br2/(CH3COO)3Ti, Cl2O/H2SO4,
N-chloro or N-bromosuccinamide.
e) Iodine reacts very slowly and iodination is carried out by I2/oxidising agent (HNO3, HIO3, SO3,
H2O etc.), I2/Cu may also be used
f ) At high temperatue, the directive influence of Cl2 and Br2 is changed, most probably due to electrophilic
substitution mechanism.
g) HALOGENATION OF THE SIDE CHAIN: The side chain halogenation of alkyl benzenes takes
place in the presence of light or high temperatures. Side chain halogenation is mostly carried out by
using the reagent N-bromosuccinimide (NBS) in the presence of light.
CH 3 O CH 2Br
| || |
h
+ NBr CCl4

|| Benzyl bromide
O
h) An alkyl benzene with side chain other than methyl may lead to the formation of more than one
products.

CH – CH3
CH2CH3 |
| Br
Br2 (I)
Heat, light
CH2 – CH2Br
(II)

Order of stability of free-radials.

Allyl > Benzyl > 3° > 2° > 1° > CH3  vinyl (from bond dissociation energy data).
2. Nitration
Benzene when heated with a mixture of (1 : 1 by volume) concentrated nitric acid and concentrated
sulphuric acid (nitration mixture) below 600 C gives nitrobenzene.
Con. H2 SO4
C6 H6  HNO3 
570 C
C6 H5 NO2  H2O
On heating the reaction mixture to about 90  100C , m-dinitro benzene is obtained

NO 2

Conc. HNO3  H 2SO4  H2O


90 100 C

NO2
m  dinitro benzene

If fuming nitricacid is used along with conc. H 2SO 4 1, 3, 5 - tri nitro benzene is obtained

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NO 2

Conc. H2SO4
 3HNO 3 100 C

fuming  O2 N NO 2

Benzene shows no nitration with dil. HNO3

Other nitrating agents can also be used depending upon nature of reactant.
(i) dil. HNO3 , (ii) Conc.HNO3 , (iii) HNO3 + CH3COOH or (CH3CO)2O, (iv) N2O5/CCl4,
(v) Esters of HNO3 / Base etc.
The role of H2SO4 in the nitration mixture is to eliminate water.
To get mono nitro benzene temperature should be maintained in between 50 to 60oC.
3. Sulphonation
Benzene undergoes sulphonation with the following reagents

Conc. H 2SO4 SO3H

fuming H 2SO4
Chloro Sulphonic acid  CCl4
SO3 in any org. solvent

The attacking electrophile is SO3 (from fuming sulphuric acid i.e., H 2 SO4  SO3 )
4. Friedel craft’s Alkylation
Benzene reacts with alkylhalide in presence of anhydrous AlCl3 and gives alkyl benzene. The reaction
is known as Friedel Craft’s alkylation reaction.
R

AlCl3
 RX   + HX

Alkyl benzene

CH3

AlCl3 + HCl
 CH 3 Cl  

CH2CH3

AlBr3
 C2 H 5 Br   + HBr

Mechanism: RX  AlX 3  R   AlX 4 

H
R
 AlX 4
R 
 R  

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Attacking electrophile is R 
Friedel-Crafts alkylations are not restricted to the use of alkyl halides and AlCl3 .
Many other pairs of reagents that form carbocations (or carbocation like species) may be used as well.
These possibilities include the use of a mixture of an alkene and an acid.
CH(CH3) 2

O C
 CH 3 — CH  CH 2 
HF

propene
Isopropyl benzene
A mixture of an alcohol and an acid may also be used.
60 C
 HO 
BF3


Alkylating agents are

a) RX/Lewis acid b) Alkene/protonic acid c) ROH/H+
Two types of catalyst are used:
a) Lewis acids : Anhydrous AlCl3, AlBr3, BF3 etc.
b) Protonic acids : H2SO4, HF etc.
Order of reactivity : RF > RCl > RBr > RI
Order of activity of Lewis acids is
AlBr3 > AlCl3 > CaCl2 > FeCl3 > SnCl4 > BCl3 > BF3 > ZnCl2
With higher alkyl halides, the product is rearranged due to formation of more stable carocation.
CH3 CH CH3

AlX
 CH3 CH 2 CH 2 X 3 + HX

Reaction is not possible if deactivating groups like

-NO2, -COCH3 etc.
are attached to aromatic ring.
5. Friedel - Craft’s Acylation
The reaction of benzene with an acyl halide (or) acid anhydride in presence of Lewis acid as catalyst to
give acyl benzene is known as Friedel - Craft’s acylation.
COR

Lewis acid
 RCOX   + HX

COCH3

AlCl3
 CH 3COCl   + HCl

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COCH 3

AlCl
+ (CH 3 CO)2 O  
3
 + CH 3COOH
Mechanism:
O O

R  C  X  AlX 3  RC   AlX 4 
H
COR
COR AlX 4
 RC  O 
    AlX 3 +HX


Electrophile is acylium cation (R C O)
Acylating agents:
i) RCOX/Lewis acid
ii) RCOOH or (RCO)2O or CH2 = C = O/Lewis acid
Solved Problem: Identify the product formed when benzene reacts with (CH3)3C - COCl in
presence of AlCl3. Explain the reason.
Solution : Product formed by (CH3)3C - COCl and benzene is not PhCOC(CH3)3.
 
Reason : Less stable (C H 3 ) 3 C O decomposes to more stable (CH3 ) 3 C . Hence
alkylation takes place instead of acylation.
Hence product formed is t-butylbenzene. Ph-C(CH3)3
Applications of Friedel craft’s reaction.
Friedel - craft’s acylation : Used to prepare phenyl ketones by introducing acyl group.
COCl

AlCl3 Benzoylchloride

C6 H 6 +COCl2  
Electrophile :C OCl
Phosgene

CONH 2

AlCl3
 ClCONH2   Benzamide

AlCl3 CH 2
2  HCN  HCl  

diphenyl methane

AlCl3
3  CHCl 3   CH

Triphenyl Methane

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Disadvantages :
1. Easy to prepare methyl, ethyl or isopropyl benzenes but difficult to introduce n - propyl (or) n - butyl
group. The reason is rearrangement of carbonium ion to give a more stable carbocation. The order of
stability is 3  2  1 .

CH 3CH 2 CH 2 
Rearrangement
 CH 3  CH  CH 3

2. An aromatic ring less reactive than that of halobenzene don’t undergo Friedel Craft’s reaction. Aromatic
ring containing - NH2 , –NHR,  NR2 , groups does not undergo friedel craft’s alkylation due to formation
of anilinum complex which is meta directing and has more electron withdrawing power than halogen in
benzene ring.

H H
+
H N H N AlCl3

 AlCl3 


meta directing group and

does not go Friedal
Craft's reaction

3. Aryl and Vinylic halides cannot be used as the halide component because they do not form carbocations
readily.

Cl

No reaction
AlCl3
 
No reaction

Cl

4. Polyalkylations often occur - Alkyl groups are electron releasing groups, and once one is introduced
into the benzene ring it activates the ring towards further substitution.

CH(CH3)2 CH(CH3)2
H 3C
BF3
 CHOH
60C
 
H 3C 24% Isopropyl benzene
CH(CH3)2
14% diisopropylbenzene

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Addition reactions
Benzene undergoes addition reactions under special conditions.
6. Hydrogenation
At high temperature and pressure, in presence of finely divided nickel benzene undergoes hydrogenation
to give cyclohexane.

Ni/150o C
 3H 2 
25 atm
cyclohexane
In presence of Pt, reaction occurs at room temperature
7. Birch Reduction

H H
Na / Lid. NH3
 4 H 
C H OH

2 5

H H

Na / Liq. NH3

C H OH

2 5

Na /Liq. NH3

C2 H 5OH


OCH 3 OCH 3 O

Li H3 O

liq. NH , EtOH
 
H O

3 2

Methoxy benzene 1  Methoxy  1, 4  2  Cyclohexenone

(anisole) cyclohexadiene (84%)

8. Addition of Chlorine
Benzene reacts with chlorine in presence of sunlight to give benzene hexachloride (BHC) or
hexachlorocyclohexane or Gamaxene or 666 or Lindane.
Benzene reacts with chlorine or bromine in presence of sunlight or ultraviolet light and in absence of
halogen carrier (such as FeCl3 & AlCl3 etc) to produce crystalline hexachlorides and hexa bromides
respectively.

Cl
Cl Cl
hv
 3Cl2 
Cl Cl
Cl
Benzene hexachloride (BHC)
 - isomer is Gammaxene (or) 666 (or) lindane
BHC is a powerful insecticide

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9. Ozonolysis
One mole of benzene reacts with three moles of ozone to give a triozonide, which on hydrolysis
inpresenof zinc gives three moles of glyoxal.
O
O
O
3 O3 O H2O / Zn
OO 3 HC CH
O + 3H2O2
O O
Benzene Benzene triozonide Glyoxal
O
C6H6(O3)3
O

Zn dust destroys H2O2 which may oxidise glyoxal

Above addition reactions of benzene prove the presence of three double bonds in benzene but they
are different from aliphatic double bonds in following reactions:
i) Benzene does not decolourise Br2 / H 2O or cold alk.KMnO4
ii) Benzene does not give addition reaction with HX or HOX
10. Oxidation
Benzene is a stable compound it is not attacked by ordinary oxidising agents (acidified - KMnO4
chromic acid)
Strong oxidising agents convert benzene slowly into CO2 and water. On heating, being inflammable
liquid it burns in air with smoky flame (combustion)
2C6 H 6  15O2  12CO2  6 H 2O +Heat
Oxidation of side chain: Although benzene itself is not susceptible to oxidation but side chain
attached to the benzene ring undergoes oxidation and converts itself into a –COOH group. Oxidation
of side chain takes place after substance is heated for a long time with KMnO4.
R COOH
| |
KMnO 4
 

The above reaction can be used for identifying substitution pattern in aromatic compound. If any compound
gives pthalic acid on heating with KMnO4, then we can infer that it is ortho disubstituted benzene.
R COOH
| R | COOH
KMnO 4
 

Absence of a benzylic hydrogen does not favour the oxidation reaction.

CH3
|
H3C – C – CH3
|
Neutral KMnO4
  No reaction

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11. With vanadium pentoxide

Benzene is oxidised to maleic anhydride in presence of V2O5 at 4500C – 5000C
O
V2 O5
C6 H 6 +9  O    O + 2CO2 +2H 2 O
450C-500C O
12. Reduction Reactions
Benzene undergo reduction in presence of strong acid like HI

2  CH3
 2HI    6I 2

Directing Influence of Functional Groups in Monosubstituted benzene

1. In Benzene we get just one monosubstituted product in electrophilic aromatic substitution as all the
positions are equivalent. However, for substitution in a compound which already has a group
attached to the ring, three disubstituted products, (1,2), (1,3), (1,4) commonly called ortho, meta
and para respectivey are possible. These are abbreviated as o, m and p.
Y Y Y Y
E

 E 
  
E
1, 2 1, 3
ortho meta E
1, 4
para

Three products formed are not in equal amounts.

Ex: Nitration of Methyl benzene with nitration mixture at different temperatures.
CH 3 CH 3 CH 3 CH 3
NO2 
HNO3 / H 2SO4

300 K

NO 2
58% 5% NO 2
37%

NO2 NO 2 NO2 NO2

NO 2
fu min g HNO3 / H 2SO4

  
375 K
NO 2
6% 93% NO2
1%

2. To understand why a substituent directs an incoming electrophile to a particular position, we must look
at the stability of the carbocation intermediate formed in the rate-determining step.
When a substituted benzene undergoes an electrophilic substitution reaction, three different carbocation
intermediates can be formed.
The one which is more likely to be formed depends on their relative stabilities.
Comparing the relative stabilities of the three carbocations allow us to determine the preferred pathway
of the reaction because the more stable the carbocation, the less energy required to make it.

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CH3 CH3 CH3
Y Y Y
H H H
ortho


attack 
 

most stable
CH3 CH3 CH3 CH3

 Y  
meta
attack
 Y 
 Y 

Y
H H H
toluene
CH3 CH3 CH3

para

attack
 
 

H Y H Y H Y
most stable

The structure of the carbocation intermediates formed from the reaction of an electrophile with toluene
at the ortho, meta, and para positions. As the ortho & para complexes are relatively more stable hence
it is ortho, para orienting.
The structures of the carbocation intermediates formed from the reaction of an electrophile with
Benzaldehyde at the ortho, meta, and para positions.

CHO CHO
H H CHO
H
E E
Ortho  E

attack
H least stable

2 H 3
4
CHO H O H O H O
H H
E Meta 
 
attack H H
H
5 E 6 E H E
7

H O H O H O

Para 

attack H H

E 8 H E 9 H E 10
H
least stable
The sigma complex of meta attack is more stable than that of ortho and para attacks hence CHO group
is meta directing.
Thus when a group is attached to benzene ring it produces two effects
I) Activity effects II) Directing effects
I. On the basis of activity effects, groups may be divided into two types
1. Activating Groups
Which increases the activity of aromatic ring in electrophilic substitution reactions
These are of three types
a) Strongly activating groups
Ex: NH2 , - NHR, - NR2 , -OH, -O-

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b) Moderately activating groups

Ex: NHCOCH3, -NHCOR, -OCH3, -OR
c) Weakly activating groups
Ex: -CH3, -C2H5, -R, -C6H5
2. Deactivating Groups
Which deactivates the benzene ring towards electrophilic substitution reactions,
These are of three types
a) Strongly deactivating groups

Ex: -NO2, - NR3 , -CF3, -CCl3,
b) Moderately deactivating groups
Ex: -CN,-SO3H,-CO2H,-CO2R,-CHO,-COR
c) Weakly deactivating groups
Ex: -F, -Cl, -Br, -I
II. On the basis of directing properties groups may be of two types:
1. Donation of electrons into a benzene ring by resonance : If group attached the benzene ring is
electron releasing group it enhances electron density at ortho and para positions by either +R effect or
+I effect. Meta position doesn’t get any electron density.
Ortho, Para - Directing Groups
Groups Like -R, -OH, -OR, -SH, -NH2,
-SR, -NHR, -NR2, -CH2R, -C6H5, -X, -CH2OH,
-CH2Cl, -CH2NH2, -CH2CN, -CH2COOH,
-CH = CH-COOH, -CH = CH2
release electrons to the benzene ring makes the benzing ring electron rich at ortho and para positions.
These positions are more susceptable to the attack of electrophiles. Hence these groups are called
ortho and para directing or Ring activating groups
Ex: Anisole (methoxy benzene) where methoxy group is EDG. The resonance structures show electron
density at ortho and para positions facilitating incoming electrophile to ortho or para position.
OCH3 OCH3 OCH3 OCH3 OCH3 OCH3

Ortho and Para position get -ve charge

indicating electron density
In the para attack of electrophile
OCH3 OCH3 OCH3 OCH3 OCH3 OCH3

E+ H H
E H E E H E E
In the ortho attack of electrophile
OCH3 OCH3 OCH3 OCH3
E+ E E E OCH3 OCH3
E
H H E
H H

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In the meta attack of electrophile

OCH3 OCH3 O CH 3 OCH3

H H H
E+
E E E
R e la tiv e ly le ss S ta b le

a) Greater the number of possible cannonical structures greater will be the dispersal of charge and
greater will be the stability of arenium ion.
b) In ortho or para attack of electrophile, four resonance forms are possible
while in the attak of electrophile at meta position, only three cannonical forms are possible.
Hence, ortho, para directing group stabilises the ring to greater extent.
c) Ortho and para positions get more electron density through resonance.
d) Inductive and resonance effects in the orientation : Group like halogen which deactivates by
–I effect but activates by Resonance. But the overall electron density increases at ortho and para
positions of the ring due to resonance. The electrophile attacks at these positions giving rise to ortho
and para disubstituted compounds.
Cl
Cl Cl
NO2
Nitration

 +
NO2
e) Presence of o- and p - directing groups (activating groups) facilitate nitration even with dilute
HNO3 otherwise not possible.
Ex:.
OH OH OH
NO 2
dil. HNO3

 H2SO4


NO 2
Ortho and Para nitrophenols
2. Removal of electrons from a benzene ring by resonance: If group attached to benzene ring is
EWG, it withdraws electrons particularly from ortho and para positions thereby meta position appear
relatively more electron dense. Thus, these groups are referred as meta directing or ring deactivating
groups.
Meta Directing Groups
NO2, -SO3H, -SO2H,-SO2Cl,-CHO, -COCl,-COOR, -COR, -COCOOH,-CX3,
  
 N H 3 ,  N HR 2 ,  N R 3 etc.
NO2 NO2 NO 2 NO2

NO 2
fu min g HNO 3 / H 2 SO 4

  
375 K
NO2
6% 93% NO2
1%
Presence of m - directing groups (deactivating groups) slow down nitration.
Ex: Higher temperatures are required to get di nitro and tri nitro substituted benzenes.
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Solved problem: Write down the relative rate order of monobromination of the following
compounds and assign reasons for the order.
PhNH2, PhCOOH, PhH, PhBr, PhNO2, PhCH3
Solution : Among the given compounds
a) PhNH2 and PhCH3 have activating groups, —NH2, and —CH3 respectively.
NH2 has a strong +R-effect and CH3 has +I-effect and hyperconjugative effet.
+R effect being stronger than the +I and hyperconjugative effects, PhNH2 will undergo
the reaction more readily than PhCH3.
b) PhCOOH, PhBr, PhNO2 have deactivating groups
The order of increasing deactivating effects is Br  — COOH  —NO2
c) PhH has neither a deactiving nor an activating group
So it will be more reactive than the compounds with deactivating groups.
Therefore, the decreasing rate order is:
PhNH2  PhCH3  PhH  PhBr  PhCOOH  PhNO2
Uses of Benzene
1. It is used as solvent for fats and resins.
2. It is used in drycleaning.
3. It is used in the synthesis of phenol, styrene, aniline, insecticides like BHC.
4. It is used as a motor fuel.
Korner’s Rule of Orientation
This rule is used to find out orientation of disubstituted benzenes when the two substituents are
identical. According to this rule ,ortho disubstituted benzene will give two types of derivatives,meta
gives three types of derivatives and para gives only one.
Carcinogenicity and toxicity
1. Benzene and several polynuclear hydrocarbons like 1,2-benzanthracene, 3-methylcholanthrene,
1,2-benzpyrene ,1, 2, 5, 6- Dibenzanthracene are toxic and said to be carcinogenic
2. Most of these are formed due to incomplete combusion of tobacco, coal, petroleum etc.
3. They undergo various biochemical changes in human body and finally damage DNA to cause cancer.

H3C

1,2–Benzanthracene 3–Methylcholanthrene 1,2–Benzpyrene 1,2,5,6–Dibenzanthracene

CH3

CH3
9,10–Dimethyl –1,2–benzanthracene

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Extra methods of preparation of Benzene

1. By Aromatisation

Pd / C
Pt /6000 C
a) n  Hexane 
 C6 H 6  4 H 2 b) C6 H 6


Pd / C Pd / C
c) C6 H 6 d) C6 H 6
 

 
CH 2  CH  CH  CH 2  CH 2  CH 2  Diels Alder reaction
   

e)  Pd / C

C6 H 6
2. From clorobenzene
Ni  Al alloy
C6 H 5  Cl 
NaOH /    C6 H 6
3. From Benzaldehyde

C6 H 5  CHO 
 Ph3P
3
RhCl
DeCarbonylation  C6 H 6
4. From Benzenediazonium chloride:
  H PO /  or
3 2
C6 H 5  N  N Cl 
  C6 H 6
C2 H5OH , or Na2SnO2 / O H

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Additional information

1. Applying the methods to determine the directing nature of the NH2 group.
The three possible -complexes are:
NH2 NH2 NH2 NH2
H H H H
Ortho  E E E  E


attack H
 
 
1 2 3 4
H Extra-stable

NH2 NH2 NH2 NH2

E
 Meta 
  H
attack H 
 H
H


H
H E 6
5 E 7 E

NH2 NH2 NH NH2

Para 


attack

  H
 H

H
E H E H E H E H
8 9 10 11
Extra-stable

Ortho and the Para sigma complexes has one extra resonating structure (4 and 10 respectively) in their
resonance structures. These structures are extra-stable since all the C and N atoms are in the octet
state. These two structures bring extra stability to the ortho and the para complexes. Therefore two T.S.
for the o-attack and that for the p-attack will have lower energy than the T.S. for the m-attack.
As a consequence the rates of reaction at the o- and p-positions will be greater than the rate of
reaction at the m-position which will lead to form predominant o/p-products.
2. Applying the methods to determine the directing nature of the protonated aniline.
The structures of the carbocation intermediates formed from the reaction of an electrophile with protonated
aniline at the ortho, meta, and para positions.

NH 3 NH 3 NH 3
Y Y Y
ortho H H H

attack
 
 

least stable

NH 3 NH 3 NH 3 NH 3

 Y  
meta
 Y 
 Y 

attack Y
protonated
aniline
H H H
NH 3 NH 3 NH 3

para

attack
 
 


H Y H Y H Y
least stable
The sigma complex (Carbocation Intermediate) of meta attack is relatively more stable than that of the
ortho para attacks. Hence   NH 3  is meta directing.

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3. When elecrophilic substitution reactions are carried out on a benzene derivative containing an ortho-
para directing group, the ratio of the yield of the ortho-product to that of the para-product is found to
vary from reaction to reaction and substrate to substrate.
a) Since there are two o-positions and one p-position relative to the substituent in a monosubstituted
benzene, it may seem that the o/p ratio will be 2 : 1 in all reactions irrespective of any substituent.
b) But, this is not true. The products never form corresponding to that ratio.
c) Several factors need consideration to explain the o/p ratios observed in aromatic substitution
reactions. The factors are:
i) Steric effect
ii) Electronic effects of the substituent already present in the benzene ring
iii) Interaction between the substituent and the attacking electrophile
iv) Effect of temperature
v) Solvation effect
Ex: When alkylbenzenes are nitrated under the same set of conditions, the o/p-ratio is found to be
the highest in the case of toluene and the lowest in the case of t-butylbenzene as shown in the
table.
o / p Ratios of the Nitration of Alkylbenzenes
Substituent % of o-product % of p-product o/p ratio
Me 58 37 1.57
Et 45 49 0.92
i-Pr 30 62 0.48
t-Bu 16 73 0.22
This reveals that as the volume of the substituent (alkyl group) increases down the series (Me to t-Bu)
the yield of o-nitroproduct decreases and that of the p-nitroproduct increases and as a consequence
o/p-ratio decreases.
4. Effect of increasing bulkyness of the alkyl group in ortho substitution:
Ex: Alkylation of toluene by the Friedel-Crafts reaction and the % of o-product by increasing the
bulkyness of the alkyl group
Attacking electrophile % of o-product
Me 53.8
Et 45.0
i-pr 37.5
t-Bu 0

5. Effect of increasing bulkyness of the electrophile in o / p substitution:

Ex: SE reaction on chlorobenzene and the o/p-ratio by increasing bulkyness of electrophile

A ttackin g % of % of
Pr ocess o/p-ratio
e lec trophile o-pr oduct p-produ ct
Chlorination C l+ 39 55 0.71
Nitration NO 2 + 30 70 0.43
+
Bromination Br 11 87 0.14
Sulphonation SO3 1 99 0.01

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6. The steric-factor alone should not be held responsible for the observed o/p-ratio in different reactions.
The electronic effects should also be considered among other factors.
Ex: Electronic effects and the o/p-ratio in the nitration of halobenzenes
When halobenzenes are nitrated under the same set of conditions, the yield of o-product increases
and that of the p-product decreases despite the increase in the size of the substituents, F to I, as
shown in the table.
Increasing Decreasing Substituent % of % of o/p-
Volume –I effect o-product p-product ratio
F 12 88 0.14
Cl 30 69 0.44
Br 37 62 0.60
I 38 60 0.63

–I effect of the halogen groups is supposed to be responsible for the observed o/p-ratios as shown in
the table. The –I-effect decreases on going from F to I as the electronegativity of the group decreases.
7. Mechanism of o and p-directing groups: The o- and p-directing groups (except alkyl and COO–)
have unshared pair of electrons on the atom attached on benzene nucleus.
The mechanism is therefore discussed in terms of two aspects.
a) Mechanism of o- and p-directing groups not have unshared pair of electrons:
Consider an alkyl group attached on C6H6 nucleus. It is an electron repelling group. The +I.E. of
alkyl group and + Electromeric effect along with + Mesomeric effect give rise to an increase in
electron density at o- and p-positions and thus provide site for electrophile to attack these centres.
This can also be explained in terms of hyperconjugation.

R R R R

b) Mechanism of o- and p-directing groups having unshared pair of electron(s):

Consider –OH group attached on C6H6 nucleus having two unshared pair of electron on O atom.
One of the such unshared pair of electron shifts towards nucleus following +E effect and +M effect
and give rise to an increase in electron density at o- and p-position and thus provide seat for electrophile
to attack these centres.
+ + +
O H O H O H O H

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8. Mechanism of m-directing groups:

The m-directing groups except CCl3, either possess a –ve charge or the atom of such group attached to
nucleus has a multiple bond on it. The –E, –M and –I effect of all such groups leading the displacement
of the electrons away from the nucleus and withdraw the electron from o- and p-position, thereby
producing a decrease in electron density at o- and p-position.
The electron density at meta position remains unchanged, and hence the relative electron
density at meta position appears to be more and thus electrophile attacks m-positions in all
such cases.
O O O O O O O O
N N N N

Note: The meta position electron density remains unaffected in presence of m-directing groups and
thus these groups provide no extra facility for electrophile. On the contrary they deactivate the
ring for further substitution. Hence the presence of m-directing group on benzene nucleus give
rise to SE reactions with difficulty in comparison to benzene itself.
9. Competitive orienting effect of two substituents
a) Two groups reinforce (provide same place for SE reaction) each other : Electrophilic attacks
o- and p- positions of each CH3 group, which are same and only one possible product is formed.
o rth o Me Me
E
o rth o to bo th
E+

Me Me
Para
b) Electrophile attacks o- and p-positions of CH3 group and m-positions of –NO2 group which are
same and only one possible product is formed.

Me o rth o to M e Me

E
+
E

m eta to N O 2
NO2 NO2

10. Two groups, one o/p-directing and one meta directing provides different positions for SE reactions:
The o- and p-directing group activates the ring by supplying electrons at o- and p-positions, whereas
m-directing group deactivates ring by withdrawing electrons from o- and p-positions. In such cases the
power of o- and p-directing group overpowers the m-directing group
ortho to M e Me ortho to M e Me Me Me
para to NO 2 1 and NO 2
NO 2 O2N
6 2
N O2
Nitration mixture + +
5 3

4 N O2 NO 2 NO 2 N O2
para to M e NO 2
m eta to NO 2 ortho to NO 2

Me group supplies electrons to 2,6 and 4 positions

NO2 withdraws electrons from 2,6,4 positions.

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The power of CH3 group predominates and no substitution occurs at m-position of –NO2 group.
Hence following compound is not formed.

Me

O2 N NO2

11. Two o- and p-directing groups – one is strong activating and other one is weak:
The o- and p-directing group having strong nature to supply electron pair and o- and p-position
overpowers the effect of other o- and p-directing group having weak nature to supply electron pair at
o- and p-position
Ex: OCH3 is relatively stronger o- and p-directing group than methyl group and thus substitution
occurs with respect o- and p-positions of OCH3 group.
No substitution at o-position of CH3 group.
p-position is not vacant for OCH3 group and thus only at o-position substitution occurs.

Me
Me
o rth o to M e o rth o to M e

N itratio n m ix tu re

o rth o to O M e o rth o to O M e NO2

OM e
OM e

12. Two weak activating or deactivating groups or two strong activating or deactivating groups
are present:
All possible isomers are formed.
Solved problem : Synthesize o-bromotoluene from toulene.
Solution:
CH3 CH3 CH3 CH3
Br Br
HCl
H 2S O 4
     F e / B r2   
1 50 o C

SO 3 H SO 3 H
Solved Problem :Find the product
CHO

KMnO 4
Product

Solution:
CHO COOH

KM nO4

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QUICK REFERENCES
1. Huckel rule: Compound having 4n + 2 delocalized  electrons is called aromatic compound where n
must be zero or any wholenumber.
2. Benzene and some heterocyclic compound i.e. pyrrole, furan, thiophene and pyridine also exhibit
aromaticity.
3. Aromatic compound have a tendency to give electrophilic aromatic substitution reaction.
4. In Friedel-Craft reaction, generally AlCl3 give rearranged product while FeCl3 give unrearranged product.
5. Friedel-Crafts reaction do not occur when powerful electron with-drawing groups for example NO2 is
present.
6. The amino groups –NH2, –NHR and NR2 changes into powerful electro-withdrawing groups by the
Lewis acids used to catalyze Friedel-Crafts reactions.
7. Nitro benzene is better solvent for Friedel-Crafts reaction rather than benzene due to less reactivity.
Due to strong withdrawing effect.
8. In case of nitration HNO3 behave as base while H2SO4 behave as an acid.
9. In case of Sulfonation all steps are reversible. (Deprotonation step is the slow rate-determining step).
  
10.  OH,  R,  OR,  NH2 are called activating group and ortho-para director..
 
11. —NR3+, —NO2, —CN, —SO3H, —COOH, —CHO, RCO- ,—X etc. are called deactivating group
and except halogen all group are meta director.
12. The side chain halogenation of alkyl benzene takes place in the presence of light or high temperatures.
In case of oxidation of side chain there must be benzylic hydrogen on benzene.

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