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CHEMISTRY
AROMATICCOMPOUNDS
INTRODUCTION
(1) There were alarge number of compounds which were obtained fromnatural sources, e.g. resins, balsams,
'aromatic' oils, etc., which comprised a group of compounds whose structures were arbitrarily classified as
aromatic (Greek : aroma, fragrant smell) compounds.
(2) These compounds contained a higher percentage carbon content than the corresponding aliphatic
hydrocarbons, and that most of the simple aromatic compounds contained at least six carbon atoms.
It was shown that when aromatic compounds were subjected to various methods of treatment, they often
produced benzene or a derivative of benzene.
(3) The benzene containing aromatic compounds are called benzenoid compounds, these are cyclic, but
their properties are totally different from those of the alicyclic compounds.
(4) Benzene was first synthesised by Berthelot (1870) by passing acetylene through a red-hot tube :
3C
2
H
2
C
6
H
6
+ other products
(5) It is mostly prepared by the decarboxylation of aromatic acids, e.g. by heating benzoic or phthalic acid
with calcium oxide / (soda lime).
COOH

) CaO ( NaOH

) CaO ( NaOH
1. Aromatic Character : [The Huckel (4n + 2)t rule]
The following three rules are useful in predicting whether a particular compound is aromatic or nonaromatic.
1. Aromatic compounds are cyclic and planar.
2. Each atom in an aromatic ring is sp
2
or sp hybridised.
3. The cyclic t molecular orbital (formed by overlap of p-orbitals) must contain (4n + 2)t electrons, i.e.,
2, 6, 10, 14 ........ t electrons. Where n = an integer 0, 1, 2, 3,..............
Molecular orbital theory of aromaticity
According to molecular orbital theory benzene is a regular flat hexagon. Thus each carbon atom is in a
state of sp
2
hybridisation. Hence, in benzene, there are six oCHbonds, six oCCbonds and 3CCt-bonds
six 2p
z
electrons (one on each carbon atom) are present in 2p
z
orbitals, which are all parallel the p-orbitals
are perpendicular to the plane of the ring. These electrons can be paired in two ways, both being equally
good (b and c). Each 2p
z
electron, however, overlaps its neighbours equally, and therefore all six atomic
orbitals a single hexacentric molecular orbitals.
(a) (b) (c) (d)
In the ground state, the total energy of the three pairs of delocalised t-electrons is less than that of three
pairs of localised t-electrons (b) or (c), and hence the benzene molecule is stabilised by delocalisation
(resonance).
2. Comparison of Aromatic compounds with alkenes
Benzene is not as reactive as alkenes, which react rapidly with bromine at roomtemperature to give addition
products. For example, cyclohexenereacts togive trans-1, 2-dibromocyclohexane. This reaction is exothermic
by about 29 kcal/mol (121 kJ/mol.)
+ Br
2
AH = 29 kcal ( 121 kJ)
The analogous addition of bromine to benzene is endothermic because it requires the loss of aromatic
stability. The addition is not seen under normal circumstances. The substitution of bromine for a hydrogen
atom gives an aromatic product. The substitution is exothermic, but it requires a Lewis acid catalyst to
convert bromine to a stronger electrophile.
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CHEMISTRY
+ Br
2
AH = + 2 kcal (+ 8kJ)
+ Br
2

3
FeBr
+ HBr AH = 10.8 kcal ( 45 kJ)
Examples of Aromatic Compounds : (Table )
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3. Aromatic Electrophilic Substitution (ArS
E
2) Reactions in Benzene Ring
Like an alkene, benzene has clouds of pi electrons above and below its sigma bond framework. Although
benzenes pi electrons are in a stable aromatic system still they are available to attack a strong electrophile
to give a carbocation. This resonance-stabilized carbocation is called a sigma complex because the
electrophile is joined to the benzene ring by a new sigma bond.
Thesigma complex (also called anareniumion) is not aromatic because thesp
3
hybridcarbon atominterrupts
the ring of p orbitals. This loss of aromaticity contributes to the highly endothermic nature of thus first step.
The sigma complex regains aromaticity either by a reversal of the first step (returning to the reactants) or by
loss of the proton on the tetrahedral carbon atom, leading to the substitution product.
Theoverall reaction is thesubstitutionof anelectrophile

) E ( for a proton

) H ( onthe aromatic ring: electrophilic
aromatic substitution.
Step 1 : Attack of an electrophile on benzene ring forms the sigma complex
H E
H E
Resonance hybrid
[ o complex]
Arenium Ion
Step 2 : Loss of a proton gives the substitution product.
H E

O
: Nu
E
+ Nu H
4. Activating Groups or Electron Releasing Groups (ERG)
All groups having one or more lone pair of electrons are activating groups because they release electrons
towards the nucleus increasing electron density and hence energy of the system. Reaction rate is increased
due to low energy of activation. Examples :
> > > > > OR > > Ar > R
All the groups which are electron donating etc. are orthopara directing and
facilitate electrophilic substitution in the benzene ring.
Ex.1 Compare the activating effects of the following o, p-directors and explain your order
(a) OH
..
..
,
O:
..
..
-
,
OC CH
3
..
..
||
O
(b)
2
. .
H N and
O
||
CH C H N
3
. .

Sol. (a) The order of activation is O
-
> OH> OCOCH
3
. The O
-
, with a full negative charge, is best able to
donate electrons, there by giving the very stable uncharged intermediate
E
H
O
In
3
OCCH
||
O
, the C of the C = O
o o
+ -
has a positive charge and makes demands on the
. .
. .
O for electron
density this cross-conjugation diminishes the ability of the too donate e
s
to the arenium ion.
(b) The order is NH
2
> NHCOCH
3
because of cross - conjugation in the amide, Ar N = C CH
3
| |
H :O:
..
-
.
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5. Deactivating Group or Electron Withdrawing Group (EWG)
Such groups have tendency to withdraw t electrons from the benzene nucleus and thus decreasing its
electron density are known as deactivating groups.
Due to decrease in electron density of the ring, the rate of electrophilic substitution is retarded. These groups
develop positive charge at ortho and para positions leaving the meta-positions as the point of relatively high
electron density and hence the electrophilic substitution occurs at mposition, not at oand ppositions.
eg.
6. Halogenation
(a) Bromination of Benzene :
Bromination follows the general mechanism for electrophilic aromatic substitution. Bromine itself is not
sufficiently electrophilic to react with benzene, but a strong Lewis acid such as FeBr
3
catalyzes the reaction.
Step 1 : Formation of a stronger electrophile.
Br :
:
: Br + FeBr
3
:
:: Br :
:
: Br
:
:
+
o
FeBr
3
:

o
Step 2 : Electrophilic attack and formation of the sigma complex.
Br :
:
: Br FeBr
3
:
::
+ H
H
H
H
H
H

+ FeBr
4

Step 3 : Loss of a proton gives the products.

Br
H
H
H
H
H
bromobenzene
+ HBr + FeBr
3
+
H
intermediate products
reactants
energy
reaction coordinate
BrFeBr
4
Br + HBr
+ FeBr
3
T .S
2
-10.8 kcal/mol
+ Br
2
+ FeBr
3
T .S
1
Formation of the sigma complex is rate determining and the transition state leading to it occupies the
highest-energy point on the energy diagram. This step is strongly endothermic because it forms a non-
aromatic carbocation. The second step is exothermic because aromaticity is regained and a molecule of
HBr is evolved. The overall reaction is exothermic by 10.8 kcal/mol (45 kJ/mol.)
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(b) Chlorination of benzene
Chlorination of benzene works much like bromination, except that aluminum chloride (AlCl
3
) is most often
used as the Lewis acid catalyst.
+ Cl
2
3
AlCl
+ HCl
Iodination of benzene
Iodination of benzene requires an acidic oxidizing agent such as nitric acid. Nitric acid is consumed in the
reaction, so it is a reagent (an oxidant) rather than a catalyst.
+
2
1
I
2
+ HNO
3
+ NO
2
+ H
2
O
Iodination probably involves an electrophilic aromatic substitution with iodonium ion

) (I acting as the
electrophile. The iodonium ion results from oxidation of iodine by nitric acid.

H + HNO
3
+
2
1
I
2

ion
iodonium

I
+ NO
2
+ H
2
O
7. Nitration
Nitration is brought about by the action of concentrated nitric acid or a mixture of concentrated nitric acid and
sulphuric acid often called nitrating mixture. HNO
3
alone is a weak nitrating agent where as the mixture is
strong nitrating mixture when concentrated HNO
3
and concentrated H
2
SO
4
are mixed to form the nitrating
mixture, NO
2
+
(Nitronium ion) is produced as follows :

O H
3
+
HNO
3
+ 2H
2
SO
4
Now, the NO
2
+
ion attacks the benzene nucleus and forms an intermediate cation (a benzenonium ion) which
loses a proton to yield the nitro derivative.
+
NO
2
(t-complex)
H
NO
2
+
(o - complex)
H
+
+
8. Sulphonation
The electrophilic reagent, SO
3
, attacks the benzene ring to form the intermediate carbocation.
2H
2
SO
4
SO
3
+ +
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Sulphonation, is reversible and takes place in concentrated sulphuric acid.
+ SO
3
+

H
+
+
H
+ H
Energy
progress of the reaction
+
+
SO H
3
SO H
3
SO H
3
transition state for the rate-determining step
in the forward direction and for the
rate-determining step in the reverse direction
9. Friedel Craft reaction
(a) Alkylation : The carbon atom of alkyl halides,
+
o o
X R
, is an electrophile. The presence of a Lewis acid
catalyst is also required. Anhydrous aluminium chloride. AlCl
3
, being a Lewis acid, accepts a lone pair of
electrons from halogen (Chlorine atom) of R . This makes R(alkyl) group to be sufficiently polar so as to
act as an electrophile. The mechanism for Friedal Crafts reaction involves the following steps.
(i)
(ii)
(iii) + AlCl
4

Nature of Lewis acid as catalyst

The order of effectiveness of Lewis acid catalyst has been shown to be
AlCl
3
> FeCl
3
> BF
3
> TiCl
3
> ZnCl
2
> SnCl
4
Ex.2 What would be the major product of a friedal-Crafts alkylation reaction using the following alkyl halides ?
(a) CH
3
CH
2
Cl (b) CH
3
CH
2
CH
2
Cl (c) CH
3
CH
2
CH(Cl)CH
3
(d) (CH
3
)
3
CCH
2
Cl (e) (CH
3
)
2
CHCH
2
Cl (f) CH
2
=CHCH
2
Cl
Sol. (a) Ethylbenzene (b) Isopropylbenzene (c) Sec-butylbenzene
(d) Tert-pentylbenzene (e) Tert-butylbenzene (f) 3-Phenylpropene
(b) Acylation : Acylation of benzene may be brought about with acid chlorides or anhydrides in presence of
Lewis acids.
Mechanism
Step 1 : Formation of an acylium ion.
R C Cl AlCl
3
||
O
: :
+
- ..
..
complex
-
AlCl
4
+
Step 2 : Electrophilic attack.
O
||
C
|
R
+
+
O
||
C
R
H
H
sigma complex
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Step 3 : Loss of a proton. Complexation of the product.
+
-
O
||
C
R
H
H
sigma complex
:Cl AlCl
3
..
..
e.g. +
(1) AlCl
3
(2) H O
2
Note : Friedal - Crafts acylations are generally free from rearrangements and multiple substitution. They do
not go on strongly deactivated rings.
e.g.
10. Structure of Benzene
Analysis and molecular-weight determinations showthat the molecular formula of benzene is C
6
H
6
. It is to be
expected that benzene would exhibit marked 'unsaturated reactions'. This is found to be so in practice, e.g.
(i) Benzene adds on halogen,the maximum number of halogen atoms being six.
(ii) Benzene may be catalytically hydrogenated to cyclohexane at higher temperature (200C).
(iii) Benzene forms a triozonide C
6
H
6
(O
3
)
3
.
(iv) In the absence of sunlight, benzene undergoes substitution when treated with halogen.
(v) Halogen acids do not add on to benzene.
So we conclude that
(1) Benzene contains three double bonds.
(2) All the six hydrogen atoms in benzene are equivalent consequently there is only one possible mono-
substituted derivative and there are three possible disubstitution products of benzene.
11. Preparation of Arenes :
(A) Benzene
(1) By polymerisation (of Acetylene) :
3HC CH
tube iron hot d Re
(2) By decarboxylation (of Benzoic acid) :

NaOH
) CaO (
NaOH

+ Na
2
CO
3
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(3) By catalytic reforming of n-Hexane :
CH
3
(CH
2
)
4
CH
3
2
K 873 , Pt
H

2
K 873 , Pt
H 3

(4) By reduction (of Benzene diazonium Chloride) :
+ H
3
PO
2
+ H
2
O + N
2
(B) Toluene :
(1) By Friedel-Craft's reaction :
+ CH
3
Cl
3
AlCl
+ HCl
Toluene
(2) By Wurtz fitting reaction :
+ 2Na + CH
3
Br
ether dry
+ 2NaBr
Bromobenzene Toluene
(3) From Grignard reagents :
+ CH
3
Br + MgBr
2
(4) By catalytic reforming of n-Heptane :
) H (
Pt , K 873
2

) H 3 (
Pt , K 873
2

Methylcyclohexane Toluene
(C) Xylene :

3 3
AlCl , X CH
CH
3
CH
3
o-Xylene
|
+
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12. Reactions of Benzene :
Ex.3 Complete the following

4
KMnO
X
Sol.
COOH
Ex.4 Gives the products of the following reactions :
(a)
Cl
+

3
AlCl
X (b) CH
3
Cl +
OCH
3

3
AlCl
Y
(c)
3
3 3
3
CH Cl
| |
CH C HC C H
|
CH
+
H C CH CH
3 3

3
AlCl
Z
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Sol. X = phenylcyclohexane
Y =
OCH
3
CH
3
OCH
3
CH
3
O - methyl anisole p methyl anisole
Z = 1 - Isopropyl 4 (1, 1, 2 trimethylpropyl) benzene
CH
H CCCH
3 3
H CCH
3
CH
3
CH
3
H C
3
Ex.5 Predict the products (if any) of the following reactions
(a) excess +
3
3 3 3
CH
|
AlCl CH C C H
|
Cl
+

X
Isobutylchloride
(b) +
l o tan bu 1
BF OH CH CH CH C H
3 2 2 2 3

+

Y
(c)
NO
2
+
Cl
|
AlCl CH CH C H
3 3 3
+
Z
nitrobenzene (excess)
(d)
Benzene
(excess)
+
3
2 3
3
CH
|
HF CH HC C C H
|
CH
+ =
P
Sol. X =
CH C CH
3 3
|
CH
3
ter-butyl benzene
Y = or
CH
3
4-sec. butyltoluene
|
H C CH
3
|
CH
2
|
CH
2
Z = No reaction
CCHCH
3
CH
3
CH
3
CH
3
P = (1, 1, 2-Trimethylpropyl) benzene
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Ex.6 Outline a synthesis of biphenyl from benzene.
Sol.

Fe / Br
2
Br
A

Cu
(Ullmann reaction)
13. ARYL HALIDES
(A) Preparation of Aryl Halides
1. Halogenation :
+ X
2

acid Lewis
+ HX
X
2
= Cl
2
, Br
2
Lewis acid = FeCl
3
, AlCl
3
, ZnCl
2
, Zn etc.
2. Decarboxylation :

CaO / NaOH
+ CO
2
3. From Phenol :
A

5
PCl
+ POCl
3
+ HCl
(B) Mechanism of bimolecular nucleophilic substitution (ArS
N
2)
+ Nu
O
RDS
I Step


II Step
) fast ( X

O
Intermediate ion is stabilized by resonance.
- A group that withdraws electrons tends to neutralize the negative charge of the ring and so to become more
negative itself; this dispersal of the charge stabilizes the carbanion.
G withdraws electrons : stabilizes carbanion, activates
( (CH
3
)
3
, NO
2
, CN, SO
3
H, COOH, CHO, COR, X)
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- A group that releases electrons tends to intensify the negative charge, destabilizes the carbanion, and thus
slows down reaction.
G releases electrons : destabilizes carbanion, deactivates
(NH
2
, OH, OR, R)
Orientiation in nucleophilic aromatic substitution :
At para position :
At meta position :
At ortho position :
Note : If electron withdrawing group in present at ortho and para position it especially activates the aromatic
nucleophilic substitution reaction.
14. PHENOLS (ArOH) :
(A) Preparation of ArOH
(1) (2)
(3) (4)
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(5) (6)
(7)
(B) Properties of phenol
These are characteristic of monohydric phenols. Phenol is a colourless crystalline solid, m.p. 43, b.p.
182C, which turns pink on exposure to air and light. It is moderately soluble in cold water, but is readily
soluble in concentrated sulphuric acid (Liebermann reaction), when phenol is dissolved in concentrated
sulphuric acid and a fewdrops of aqueous sodiumnitrite added, a red colour is obtained on dilution and turns
blue when made alkaline with aqueous sodium hydroxide.
Phenol is used as an antiseptic and disinfectant and in the preparation of dyes, drugs, bakelite, etc.
(C) Chemical Reactions of Phenols
(1)
(2)
(3) (Major is oxidative cleavage of ring)
(4)

(p-nitroso phenol)
(5)
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(6)
(7)
(8)
(9) (Fries Rearrangement)
(10)
(11) (polymer)
(12)
(13) (14)
(15) (16)
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15. Nitrobenzene
(A) Preparation
+ HNO
3
(conc.)
(B) General properties of nitrobenzene
(i) Yellow liquid
(ii) Denser than water. Thus insoluble in water but soluble in organic solvents
(iii) b.p. = 211C
(iv) steam - volatile
(C) Chemical Reactions of Nitrobenzene
(1)
(2)
(3)
(4)
(5)
(6)
(7)
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(8)
(9)
(10)
16. ANILINE
(A) Prepartion of Aniline
(1)
(2)
(3)
(B) Chemical Reactions of Aniline
(1) (2)
(3)
(4)
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(5)
(6) (Diazotisation)
(7)
(8)
(9)
(10)
(11)
(12) (oxidation)
(13) C
6
H
5
: C N

=
(14)
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17. Benzenediazonium chloride
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
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(10)
(11)
(12)
(13)
(14)
(15)
(16)
(17)
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MISCELLANEOUS SOLVED PROBLEMS (MSPS)
Complete the following reactions :
1. (a) + HClO
4
(b) + 2 AgClO
4

Ans. (a) (b) + AgCl
Sol. Aromatic compounds are -
(i) cyclic (ii) planer
(iii) contains (4n + 2) no of t-electrons where n = o , 1,2,3 .......
(iv) does cyclic resonance between (4 n + 2) t - electrons
2. + CH
3
CH
2
CH
2
Cl

3
AlCl
Ans.
Sol. Aromatic compounds undergo electrophilic substitution reaction, and if possible then there is rearrangement
of carbocation occurs.
3. (a) +


H
(b) +
(c)
Ans. (a) (b) (c)
Sol. Since the fridel craft acylation is faster than alkylation.
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4. + H
2
SO
4

Ans.
Sol. 2H
2
SO
4
+ +
5.
Sol. +
6.
Ans.
Sol. Incase of biphenyl one ring is electron donor and other is electron acceptor.
7.

Fe / Br
2
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Sol.
8.

Fe / Br
2
Ans.
Sol. Incase of electrophilic substitution reaction stable carbonium ion intermediate is formed.
9. (a)

O H / Br
2 2 (b)
Ans. (a) (b)
Sol. (a) ion increases the reactivity towards electrophile due to increases the electron density in ring.
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10. (a)


H / KMnO
4 (b)


H / KMnO
4
Ans. (a) (b)
Sol. (a & b) In aromatic hydrocarbons if at least one benzylic hydrogen is present then by oxidation benzoic acid
is formed.
11. (a)
KOH . aq . 2
CHCl . 1
3

(b)
KOH . aq . 2
CCl . 1
4

(c)
) excess (
O H / Br
2 2

Ans./Sol.
(a) (b) (c) + 3HBr
13.
4 2
7 2 2
SO H
O Cr Na

Ans.
Sol. Oxidation of phenol with cromic acid produces a conjugated diketone known as benzoquinone.