TOPIC

04 Aromatic Hydrocarbons (Benzene)

Aromatic hydrocarbons are specialised cyclic compounds Structure of Benzene
which are known for their characteristic unique smell. Based on the following facts, structure of benzene was obtained:
(Greek Aroma = fragrance). The group is also called (i) Molecular formula of benzene is C6H6 which
arenes. indicated that it is highly unsaturated compound (it
Most of the aromatic compounds were found to contain has eight hydrogen atoms less than normal saturated
benzene ring. Benzene ring is highly unsaturated and is alkane C6Hj4).
involved in most of the reactions of aromatic forms triozonide by adding three
i) On ozonolysis it
hydrocarbon. The unsaturation of benzene ring is atoms of oxygen, that indicates the presence of three
retained. double bonds.
Benzene and its derivatives are called the benzenoid (ii) Benzene produces only one monosubstituted
compounds. However, there are many aromatic derivative, it means that all the six carbon and six
hydrocarbons also that do not have benzene ring. Such atoms present in benzene are identical.
hydrogen
compounds are called non-benzenoid compounds. e.g.
Cyclic Structure of Benzene
Kekule's Hypothesis
N On the basis of above observations in H
Benzene Naphthalene Biphenyl Pyrrole 1865, Kekule proposed the ring
(benzenoid) (benzenoid) (benzenoid) (non-benzenoid) H
structure for benzene. Kekule suggested
that the six carbon atoms of benzene
Nomenclature and Isomerism of
are in a ring and are bonded to each
Benzenoid Compounds H
other by alternating single and double
bonds. One hydrogen atom is attached H
(For nomenclature and isomerism of aromatic
compounds see chapter 12). Since, all the six hydrogen to each carbon atom of a ring.
atoms of benzene are equivalent, so it gives only one type The given Kekule structure predicts the formation of rwo
of product on monosubstitution. types of 1, 2-dibromobenzene I and II.
However, disubstitution gives three products viz 1,2 or Brk
1,6 (or otho), 1,3 or 1,5 (or meta) and 1,4 (or para). Two Br atom attached to (C=C) bond

e.g
CH3 Br
CH3
CH3 II.
T w o Br atom attached to (C-C) bond

1, 2-dimethylbenzene But only one type of 1, 2-disubstributed product is

Methylbenzene
(toluene) (0-xylene) formed. Thus, all the hydrogen atoms of benzene are

CH3 equivalent. Kekule assumed that the double bonds in the

CH structure of benzene are not fixed but are wandering in
continuous state of oscillation back and forth berween
two carbon atoms. Thus, each bond has single bond
character for some fraction of time and double bond
CH3 character for the other fraction.
CH3
1, 3-dimethylbenzene
m-xylene)
1,4-dimethylbenzene
(p-xylene) 9-
)
(0 Benzene ekules
ale's structure
benzene on
on hydrogenation in
nickel catalyst Resonance and Stability of Benzenee
the
combines with gives
three cyclohexane presence
(CH12).
of
It also
The
The
stability of benzene be explained on the basis can
benzene hexachloride. molecules of concept of resonance.
chlorine
basis of
o
on

These reactions give to

confirm the
According to Kekule, benzene is
bonds. presence of three double the two structures
a
(A) and (B) and the
resonance hybrid of
may be represented hybrid
by inserting a circle or a dotted circle
structure
CGHg+3H,-
Benzene CH2
Ni

220-250°C Cyclohexane
in the
hexagonas shown in
six electrons which are (C). The circle represent the
(i) The synthesis of delocalised between the six carbon
acetylene benzene from three
also favours
atoms of the benzene
ring.
Kekule's molecules of
structure.

(ii) Benzene combines

3CH=CHA
form triozonide. with three molecules of ozone to
(A)
--
(B) (C)
(iv) A compound with Orbital Structure of Benzene
stable than localised delocalised electrons is more In benzene,
all the six carbon atoms
electron compound. orbitals. Out of which twocontain
stability that The extra three
compound gets as a result of having
delocalised electrons
a
sp2-hybrid
or resonance energy.
is called
delocalisation sp2-hybrid orbitals of each carbon atom
overlap with
energy sp2-hybrid orbitals of
of
C-Cobonds which lie in the adjacent
C-atoms to form sixSIx
Drawbacks of Kekule's structure hexagonal
plane. The
) The unusual
remaining sp2-hybrid
orbital of each carbon atom
stability of benzene could not be overlaps with the ls-orbital of a
explained via Kekule structure. six C-Ho bonds. Each
C also has one
hydrogen
atom to
give
i) The expected heat of p-orbitalwhich is
perpendicular unhybridised
hydrogenation of Kekule
structure was 85.8 kcal/mol. But the as shown in the
to the
plane of the ring
calculated heat figure.
of
hydrogenation of benzene is 49.8 kcal/mol.
This statistics
suggests that in real sense benzene is
more stable than the
proposed Kekule structures.
The difference in these two values, i.e. 36
kcal/mol is
considered as resonance energy for benzene.
O

The
unhybridised p-orbital of each carbon atom
Cyclohexatriene laterally with the overlaps
p-orbital of adjacent carbon atom
form a Tt-bond. In to
3 6 kcal mol AH =- 85.8 kcal mol general, there
equal are two
benzenee possibilities of three T-bonds by the overlap of
AH= - 49.8 kcal mol of C-C2.C3-4, C5-C6 Fig. (a) p-orbitals
Cyclohexane
C2-C3.C4-Cs,
shown in the following C6-C, Fig.b) respectively as
figures
Progress of reaction

ii) When all the carbon-carbon bond length of benzene

molecule was measured they came
This was
equal (1.39A).
the fact that was proposed by
against
Kekule, i.c. benzene contains 3 single and 3 double
- or
bonds of bond length 1.44 and 1.36 A. (a) (b)
 Allínone ISC Chemistry Class II
582

(4n + 2) 6 and n = I thus, Huckel rule is followed.

The above fact is also supported by X-ray diffraction
which showed that all the C-C bond lengths are equal
(139 pm) and intermediate of single and double bond (c) Napthalene
lengths. The overlapping of p-orbitals of adjacent
carbon atoms can also be represented in the form of two

doughnuts (rings) of electron clouds, one

above and one
Number of n-electrons
= 10
below the plane of the hexagonal ring as shown below:
4n+ 2 10 and n = 2 thus. Huckel rule is followed

(d)

OI

Electron cloud Phenanthrene

Anthracene
Number of t-electrons = 14.
The six T-electrons are, thus, delocalised and can move
freely about the six carbon nuclei. This delocalised 14 and n 3 thus, Huckel rule is followed.
4n+2 =

T-electron cloud is attracted more strongly by the nuclei

Those compounds which does not follow the above
of the carbon atoms than the electron cloud localised
3 rules are called non-aromatic. These non-aromatic
between two carbon atoms. These delocalised t-electrons
makes the benzene ring more stable. compounds may be cyclic with conjugated system.
Further, absence of pure double bond shows the
(cyclooctatetraene) is cyclic with conjugated
non-reactivity of benzene towards usual reactions of e.g
alkenes and also explains its unusual behaviour.
system but it does not follow Huckel rule and its plane is
Aromaticity also distorted that's why it is non-aromatic.
A compound can be considered as aromatic if it follows
the given three rules:
Methods of Preparation
) An aromatic compound must be cyclic and planar. Benzene is commercially obtained from coal tar but in
laboratory, it is prepared by following processes
(ii) An aromatic compound must have the conjugated
system in it.
1. Decarboxylation of Aromatic Acids
(ii) An aromatic compound must follow Huckel's rule
(From Sodium Benzoate)
which states that the number of T-clectrons
= (4n+2); where n = integer 0, 1, 2, 3 etc. When sodium salt of benzoic acid is heated with
sodalime (NaOH + CaO), it gives benzene.
e.g
(a) Cyclopropenyl cation
COONa

A
Number of T-electrons = 2
NaOH
CaO

Benzene
Na,CO3

(4n+2)=2 and n =0 thus, Huckel's rule is followed.

2. Reduction of Phenol
When vapours of phenol are passed over heated zinc dust,
(b) benzene is obtained.
OH
Benzene
Cyclopentadienyl Cycloheptatrienyl
anion cation

Number of t-electrons = 6 +Zn ZnO

(Dust)
 583
Hydrocarbons

C+[AICl4
C+AICI4]
Physical Properties ( v ) C H - C - Í +AlCI,
CH
i) Benzene is a
colourless, volatile liquid insoluble in
water
etc.).
but soluble in
organic solvents (ether, ethannol =o ion)
II Formation of carbocation (arenium
(i) It is inflammable and burns with Step or
sooty flame. Eattacks the benzene ring to give G-complex
(iii) The melting and boiling point of aromatic on
of the carbon is
in which one
hydrocarbons increases with increasing molecular arenium ion,
mass. This is due to increase in sp-hybridised. -sp3-hybridised
Waals forces of attraction with magnitude
of van der
carbon
increase in molecular
size. Amongst isomeric arenes, the
para-isomer has
highest melting point because it is most symmetrical.
iv) They are toxic and carcinogenic in nature. H
ion)
Sigma complex (arenium
Chemical Properties The arenium ion gets stabilised by resonance.

Benzene readily undergoes electrophilic substitution

reactions and addition reactions. Important chemical H
reactions exhibited by benzene are as follows E
I. Electrophilic Substitution Reactions
The reactions in which an electrophile substitutes the
hydrogen atom of the benzene ring, are called
electrophilic substitution reactions.
Mechanism
III Removal of proton To regain aromatic
-
It involves following steps Step
character, the o-complex lose o n e proton to AlCl4 or

Step I Generation of electrophile, Et Theclectrophile shown below

generated during chlorination, nitration, sulphonation, HSO as

alkylation and acylation are respectively E

Cit, NO, sO;,R*,RCO* (acylium ion). E [AICLA +HCl+AICl3
H
(i) Cl-C+AICl CIt+CI-AIC
H E
CI* +[AICl41
Chloronium ion [HSO- +HSO4
(ii) HO,sÓ -H+H-O- NO, Various electrophilic substitution reactions are as
follows:
Sulphuric acid Nitric acid () Nitration Benzene undergoes nitration when treated
H with conc. HNO, in the presence of conc.
+ acid.
sulphuric
H-0-NO, + HSO4
NO2
Conc. H2SO4
+HNOg 323-333 KK
HO+ NO2
Nitronium ion
Protonated nitric acid Nitrobenzene
i) Halogenation Benzene undergoes chlorination or
Gii) 2H,sO, SO, +HSO +Hy0" bromination when it is treated with
+ bromine in the chlorine or
presence of Lewis acid catalyst,
(iv) CH-C+ AICl CH3 +[AICI,I aluminium chloride or ferric
bromide in the absence of chloride or ferric
light.
 Allinone ISC Chemistry Class 11
584

CI CHCH,CH,C+ AICl, CH,CH,CH

AlCI 1°(less stable)
Anhyd. AICl
Cl2 or FeCl3 Rearrangement
CH,CHCH,]
2°(more stable)
Benzene Chlorobenzene
treated with
(v) Friedel-Crafts acylation When benzene is
the presence of Lewis a
alkyl halide acid anhydride in
or

CI acid (like AlCl,), acyl benzene is obtained product.

as a

Ch
Anhyd. AIC
o-dichlorobenzene +CHCOCa A
CI
Acetyl chloride
p-dichlorobenzene COCH
If E" is in excess, further substitution takes place,
e.g. benzene on treatment with excess of chlorine in + HCI
the presence of anhydrous AlCl can be chlorinated
to hexachlorobenzene (C,Cl,). Acetophenone
CI

CI Anhyd. AlCl3
Anhyd. AlC
+6Cl2 dark, cold +6HCI (CH,CO),O-
Acetic anhydride
CI
CI
COCH
Hexachlorobenzene
(CC +CH,COOH
(i) Sulphonation It is done by heating benzene with
fuming sulphuric acid (oleum).
2. Addition Reactions
SOH ) Addition of Hydrogen When benzene is treated with
hydrogen in the, presence of nickel catalyst, under
H,SO(SO,) +HO vigorous conditions, i.e. at
high temperature and/or
Fuming pressure, it gets reduced to cyclohexane.
Benzene sulphuric Benzene
acid sulphonic acid
Ni

(iv) Friedel-Crafts Alkylation When benzene is treated +3H2

with alkyl halide in the presence of anhyd. AICl
it gives alkyl benzene. This reaction is called Cyclohexane
Friedel-Crafts alkylation. (i) Addition of Chlorine When benzene is treated with
chlorine molecules in the presence of UV light,
CH addition of Cl takes place and benzene hexachloride,
Anhyd. CH Cl or gammaxane is obtained.
AICl3 HCI
+CH,C Cl
Toluene Cl CI
+3Cl2 500 K
UV Y
CH-CH-CH3
CI Cl
+C,HCl- +HCI
or Benzene hexachloride,
CH,CHCH,CI (BHC)
 1 585
Hydrocarbons

Groups
3. O x i d a t i o n Para-directing and
ortho
L Ortho and group
at

) Catalytic Oxidation (Reaction with that direct

the incoming groups.

Benzene reacts with

controlled amount of air at Oxygent) he groups
called ortho
and
para-directing
s t r u c t u r e s

of following
are

773K in presence of a
vanadium
para-positions
hybrid
pentaoxide is
resonance

a
C8 phenol
as
catalyst to give maleic anhydride. e.g. .Ö-H
OH .ö-H
O2 CHCOOH
VOs, 773K
CHCOOH
Maleic acid

Maleic anhydride II
Similarly, naphthalene gives phthalic anhydride.
-H :-H
COOH
O2
V205, 770K
COOH
Phthalic acid
IV

CO revealed that the

The above resonating
structures clearly
C O 0

and hence,
increases ato and p-positions
electron density
Phthalic anhydride
substitution occurs mainly at these positions.
exhibit - / group that
Reaction with Ozone - O H group also
(i) However,
e x t e n t at ortho
and
Benzene reacts with ozone to form benzene triozonide reduces the electron density to some

increases at
which is hydrolysed under different conditions to give But overall electron density
para -positions.
oxalic acid, glyoxal and glycol as shown below these positions of the ring due to r e s o n a n c e . Thus,
activates the ortho and
COOH - O H is an group and
activating
for electrophilic
3 para-positions of benzene nucleus
COOH substitution. Other groups that direct the incoming
Oxidative
aydrolysis
Oxalic acid
groups at o andp-positions, i.e. activating groups are
Oxi

ny
CHO -NH2, -NHR, -NHCOCH3, OCH3,
O3 Zn +3
Reductive -CH3.-C,H, etc.
hydrolysisl CHO
Glyoxal Because of the -1-effect of halogens, the overall electron

3H,O Re LiAIH density on the benzene ring decreases. It makes

Triozonide hydrKeduct
olysis iv2e 3 CH,OH substitution difticult therefore
deactivating.
halogens are
moderately
CH,OH
But due to resonance the electron density or o-and
Glyoxal p-position is greater than that at the m-position. That's
why halogens are olp-directing group.
Functional
Directive Influence of a 2. Meta-directing Group
Benzene
Group in Monosubstituted to further
The groups that direct the
incoming group to
benzene is subjected meta-position called
When monosubstituted
three disubstituted products,
are
meta-directing groups
substitution, it may give
however, not in equal amounts.
c.g.NO2,-CN,-CH0,-COR,- -COOH,
n
general, two types of
behaviour
This
are observed. Either
behaviour
olp or

NO, group, when present at

COOR,-SO,H etc.
benzene nucleus, decreases
product is obtained predominantly. already present in the the electron density due to its strong -/-effect
Ipends uponthe nature of the group iscalled deactivating
a and hence
intuence of
the directive group. Further nitrobenzene
Dczene ring and is called resonating hybrid of following structures
is a

substituents.
 Allinone ISC Chemistry - Class

586
Topic Practice 4
Questions
Very Short Answer Type
(1Marh)
II II
1Fillin the Blanks lame.
hydrocarbon burn with
.

Aromatic
()
N (ii) When benzene is
the presence of anhydrous
alky!
treated with
AlCl3, it gives
halide in

reaction.
(ii) Complete the following
UV
BHC
CgHs 500 K
V two or
(iv) The polynuclear hydrocarbons having
toxic and have
given structures show that the overall electron rings
benzene are
The more fused

density on the benzene ring decreases and thus, the property.

electrophilic substitution becomes difficult. The electron 2 Objective Type Questions.

density on o-and p-position is comparatively lesser than from which of the
that at m-position. So, electrophile attacks at (i) Benzene is obtainedfractional distillation of
after
following oils
meta-position, i.e. substitution occurs at meta-position. coal-tar?

(a) Light oil (b) Heavy oil

Carcinogenicity and Toxicity (c) Middle oil (d) Anthracene oil
The polynuclear hydrocarbons having two or more fused Which of the following compound possesses
(ii) the C-H bond with the lowest bond
benzene rings are toxic and have carcinogenic (cancer
producing) property. These are obtained by incomplete dissociation energy?
combustion of organic materials like tobacco, coal and (a) Toluene
petroleum. They reach into the human body and undergo (b) Benzene
several biochemical reactions. They damage DNA and (c) n-pentane
cause cancer. Some examples of carcinogenic hydrocarbons (d) 2,2-dimethylpropane
are as follows Birch reduction (dissolving metal reduction) of
ii)
0-xylene gives
CH CH3
CH CH3
1, 2-benzanthracene
3-methylcholanthrene
CH3
a) (b)
CH3
CH3 CH3
CH3
9, 10-dimethyl-1,2-benzanthracene
CH3 CH3
(c) (d)

Uses (iv) Aromatisation of n-heptane by passing over

) It is used in the manufacture of styrene, gammaxene, heated Al0g and Cr03 at 773 K gives
nitrobenzene, chlorobenzene, phenol, nylon, (a) benzene (b) toluene
detergent, insecticides etc. (c) xylene (d) hepthylene
(i) It is used in dry cleaning of woollen clothes.
3 Match the groups in Column I with their o, p
(ii) Benzene is blended with petrol to improve its octane
number. and m-directing influence along with electronic
factor in Column lI and choose the correct
(iv) Benzene is used as a solvent for resins, rubbers,
option using the codes given below:
paints etc.