RPhysicsWallah

AROMATIC COMPOUNDS

doublei
Even though the bond
Benzene proposed by
resonance.

their
positions. he struc
The structures
Aromatic compounds contains high percentage or. keep on
changing
the position of nucleus remain
carbon. They burn with smoky flame, produced
is such that
structure.
fo
T h e structural

in each ofthe intermediate (

Aromatic compounds have the cyclic system and the same

is
somewhat

compound This
contains (4n+2)T electrons
[Huckel rule]. ofsuch
a
various
proposed
formulas.
state
the
Where n=0, 1,2,3, .. between
known as Resonance.

Dipropylcyclopropenium n=0 27T-electron

Perchlorate
Benzene, Pyridine, Pyrrole, n = 1 67T-electron
-O-O
C)
Furan, Thiophene etc. (B)
(A)
Napthalene 10T-electron Kekule are the two main
n-2 proposed by
Anthracene The hyhri
structures
The benzene.
n=3 147T-electron structures
of
contributing a circle ora dotted
s t r u c t u r e is
represented by inserting
Aromatic Compounds: Main Source as shown
in tigure (). The circle
line in the hexagon which are delocalized
Bituminous coal when subjected to destructive
distillation in the absence ofair [1 000°-1200°C] the chief
represents
the six
electrons

benzene of the ring

carbon atoms
between the six
constituent obtained is coal tar. data reveals that benzene isa planar
X-ray diffraction the above structures of
Fractional distillation of coal tar : Different fractions molecule. Had any
one
of
been correct. Two types of C-
are benzene (A and B)
bond lengths were expected. However, X-ray
data
Fraction Temperature Main constituents indicates that all the
six C-C bond lengths are of the
which is intermediate between C-
(a) Light ol 80-170°C Benzene, Toluene, same order (139 pm)
C-C double bond (133 pm)
Xylene etc. C single bond (1 54 pm) and
(b) Middle oil The C-C bond length in benzene (139 pm) indicates
170°-230°C Naphthalene, that each bond in benzene had acquired the
(carbolic oil) Phenol etc.
characteristics differently due to resonance. The single
(c)Heavyoil 230 270°C Cresols, Naphthalene bond acquires the characteristic of double bond and
(d Green oil 270-360C Anthracene
the double bond acquires the characteristic of single
bond, thus changing the bond lengths. This is why the
Benzene- Structure of Benzene
absence of pure double bond in benzene accountsfor
the reluctance of benzene to show addition reactions
under normal conditions, thus explaining the unusual
H behaviour of benzene.
(i) Molecular orbital theory to explain benzene
H structure : The orbital overlapping gives us better
picture about the structure of benzene. All the six carbon
atoms in benzene are sp
Discoverer : Michael Faraday hybridized. Twosp hybrid
orbitals of adjacent carbon atoms
[ii] C-hybridisation : sp overlap with sp
hybrid orbitals of each carbon atom which also overiap
[iii] Geometry- Hexagonal with s-orbital of a
etiv] Bond angle: 120 hydrogen atom to form six C-H Sigm
bonds. Each carbon atom
[vC-CBond length :1.39Åogee g is now left with on
unhybridised p-orbital perpendicular to the
[vi] C-HBond length :1.09 A the ring as shown
below
plane
Resonance and Stability of Benzene
Two moderm hypothesis had been given to explain the
stability and structure of benzene. These two theories
are
() Resonance or valence-bond theory : According to
valence-bond theory, the oscillating nature of double
/
bonds in benzene (as proposed by Kekule) is now

120
Hydroca
 PhysicsWallai
od p-orbital of carbon atoms are close
t h eu n y b r i d i s e d p
Methods of Preparation of
T-bond by lateral overlap. There are [i Benzene:
enougtnt of o r m

Isolation From Light Oil Fraction

sibilities of forming three t-bonds by Industrial
method:
qual
pverlapot
-orbitals of
p-orbital.
C-C2 C3-Cg, C C or C lil Decarboxylation of Sodium Benzoate - Laboratory
C-C respectively as shown in following
Method:
Benzene is formed by dry distillation ofsodium benzoate
with soda lime.

otho
CHCOONa+NaOH DydistlaionCH,+ Na,CO,

Reduction of Phenol:
CHOH+ZnOydistlaionCH, + ZnO
(6)
[iv Hydrolysis of Benzene sulphonic Acid: CH,SO H+
res
shown
Structures shown in the above figures correspond to
structures with localised Pi-bonds. The H,O (steam) dilHCICH,+H,SOP4
Kekule 's
distance determined between all the carbon
ntemuclear

inthe ring by the X-ray diffraction is found to be

atomsih
v Reduction of Benzenediazonium Chloride:
same
howing; there is equal ability for the p- CHN,Cl+CH,OH
the the p-orbitals
carbon atom to overlap with CH+CH,CHO+ N, + HCI
thital ofeach sodium stannite
atoms (C). This can be represented Hypophoshorus acid (H,PO,) or
afadjacent carbon also be used for
(rings) ofelectron clouds (SnCl, + NaOH) or formic acid can
intheform oftwo doughnuts reduction in place of ethanol
and one below the
id).one above the plane plane of
CHN,C+ H,PO, + HOo
as shown below:
the hexagonal ring CGH,+ H,PO, +Na +HCI
SnC
CGHN,CI +2HNaHCH+N+ HCI
NaOH
CH,N,CI+ HCOOH
CH+CO, +N, +HCI

Ivil Hydrolysis of Phenylmagnesium bromide:

CHMgBr+H,0- CgH,+ Mg(OH)Br
delocalised and free to
Thesix T-electrons are thus
are
Reduction of Chlorobenzene:
move about the six carbon nuclei,
instead of any two Ivii
Ni/ Al
CH, +NaCl+H,O
asshown in (a) and (b). This spreading of pi-electrons CH,C1+NaOH+2H
below the
ntheform of ring of T-electrons above and of t -
planeof carbon atoms is called delocalisation viil Trimerisation of Acetylene:
electrons.
ACHa NICOA+(CghsBC,H,
In benzene

H
Hydroforming ofn-Hexane:
[ix]
oxIdes CH +4H
-H CH(CH,),CHHeavy metal
H 500

Physical Properties
H 80°). having
Benzene is a colourless liquid (boiling point,
smell. It forms a colourless crystalline
The vIOcalized T-electron cloud is attracted more a characteristic
cooling. It burns with
solid (melting point, S.4)
on

Sirongly by thenuclei of the carbon atoms

than the
smoky or sooty
flame. It is lighter than water (relative
clectron cloud localise between two carbon atoms and is. immiscible with water. Being
density, 0.8790)
herefo presence of delocalised t-electrons In nonpolar in nature,
it is miseible with many organic
bezene makes it ore stable than the hypothetical solvents, like alcohol
ether, acetone, acetic acid, carbon

yclohexatriene. tetrachloride, carbon

disulphide, etc.

amon 121
 PhysicsWallah EE-CHEMSTRY
Reaction: formed in an arom.
Benzene is
Nonaromatic intermediate
reaction is known as
aromatic
Whelana
compound having very low reactivity,
a substitution
electrophilic eland
Decause it remains
unaffected by many common intermediate.

Teagents, like HCI, KOH, NaOH, KMnO4, K,Cr,O7, etc. Mechanism ofAromatic SE
reaction:

Benzene shows the following types of reactions

[a] Addition
[b] Electrophilic substitution
[c] Oxidation +E
Slow
H
Addition Reaction: H
H

1
Halogenation: Cyclic Secondary carbocation
carbocation formed is stabilised
Cyclic secondary by
C resonance.
C

3Cl3CI,h
-
H

Benzene
c H
H CI
Benzene hexachloride
Benzene hexachloride is also known by many other
names
eg, B.H.C, gammaxene, gammane, lindane 666 -H
(triple six) and
was 1,2,3,4,5,6-hexachlorocyclohexane.
found that the y isomer is a
It Fas

and very strong insecticide

pesticide, hence the names
gammaxene and
H
gammane.
2. This is called as SE mechanism i.e.; substitution
Hydrogenation electrophilic bimolecular reaction.
Nitration :

3H2
Ni/Pt/PdT NO2
Benzene Cyclohexane NO2
3. Ozonolysis: NO2
<609 609
CH=O -H OaN
Nitrobenz ene
30, CH=Ot3H,0, m-Dinitrobenzene
Benzene Glyoxal

3H,0, +3Zn 3ZnO+3H,

NO2
ElectrophilicSubstitution: NO
A continuous tcloud is spread above and below the
benzene ring. Due to this, an electrophile is attracted Fummg HSO4
towards the benzene ring. This electrophile removes 100 O2N
proton (the weaker electrophile) and take its place in
-H
NO
order to gain greater stability and forms an Electrophilic 1.2,3-Trinitr obenzene (TNB)
Substitution Product or SE product. This process is Halogenation:
called Aromatic Electrophilic Substitution.
CLCl+AlCl
Chloronium ion+CHAICla
+M CoH5-H+Ci
Stronger Weaker Electrophile CgH5-C
Benzene electrophile
electrophile Sulphonation: Chlorobenzene
Substitued benzene
(SE product)
H,SO, so, +H,o
(Conc.)
l122
Hydrocarbon
 PhysiesWallah

E-CHEMISTRY 2 ,H CICOCI Anhyd AlC

so-P $O,H Benzene
(Excess) Phosgene Benzphehione +2HCL
SO The above conversions can be carried out
by taking
Benzenesulphonic acid many other compounds in place of anhydrous
AlCl
e.g., FeCl3, FeBr3, SnCl,, ZnClh, BF3, etc.
Friedel-CraftsReaction 8. Mercuration:
replacement of
involves Benzene on heating with mercurie acetate forms
Friedel-Crafts reaction
a carbocation
of an aromatic ring by Acetoxymercuricbenzene.
hydrogen atom
in the presence of CH,COO
obtained from a compound
species
chloride.
Fridel-Crafts reaction
CH,COO
>Hg+H-CH, CH,COOH+
anhydrous aluminium CH,COOHg-CH,
out in nitrobenzene (boiling
point 211)
isalwayscarried Phenylmercurie acetate

medium and in the presence of anhydrous AlCl3. (Acetoxymercuricbenzene)

Oxidation:
[i Friedel-Crafts Alkylation:
9. Catalytic Air Oxidation:
CH, -CH,+HCI Oxidation of benzene by air in the presence of
CH +CH -ClAA Toluene
vanadium
Methyl chloride pentaoxide (V2O5) can be carried out as follows:
[i] At 300°- Phenol is obtained as the major product
CH+C,H, -Clny.ACCH, -C,H,+HCI
Ethylbenzene PH

VO5
CH, +CH,CH,CH, -CIAnhyd.AICh 3000
n-Propyl chloride
Phenol
C,H, -CH(CH,), +C,H,-CH,CH,CH, [ii] At 450°-Maleic anhydride is obtained as the major
Cumene (676) n-Propylbenzene (33%)
product.
Note: A mixture of cumene and n-propylbenzene is also
obtained on taking propylene in place of n-propyl
chloride in the above reaction. because intermediate 1 +9[0] O5
450 +2CO +2H,O
carbocation rearrange to give 2 carbocation
Maleic anhydride

2C,H,+CH,Cl Anhyd CH, -CH, -C,H,+2HCI

AICl3 Diphenylmethane 10. Silver Oxide Oxidation:
Mainlyp-benzoquinone is formed, when oxidation of
Anhyd. (CH,)CH +3HCI benzene is carried out by silver oxide and HN0.
3CH,+CHCl AICl3 Inphenylmethane

[iil Friedel-Crafts Acylation : (reaction with acyl

chloride) AgO
HNO3
+ H,O

alAcetylation:
p-Benzoquinone
CH+CH,COCI
6 Acetyl chloride Anhyd.AlC CH.COCH, +HCI
Acetophenone
11. Combustion:
2CHs +150O >12C02 +6H,O
CH+(CH,CO),o Anhyd AlC CH,COCH,
Acetic anhydride Acetophenone
Catalytic Pyrolysis:
When the vapours of benzene are passed through red-
CH,COOH
hot copper or iron tube at 600°, biphenyl is formed.
[b]Benzoylation:
CH-H+H-CH- CH, CH, +H
CH+CH,COC Antbyd AlC,
Benzoyl chloride CH.COCH +HCI
benzophenone
CARCINOGENICITYAND TOXICITYY
Benzene and polynuclear hydrocarbons containing
more than two benzene rings fused
together are toxic
Hydrocarbon
|123|
 rhysiesWalah
and said to possess
cancer-producing (carcinogelc CH
property. Such polynuclear hydrocarbons are formed
on incomplete combustion of organic materials like
tobacco, coal and petroleum. They enter into huma
body would undergo various biochemical reactions and
finally damage DNA and cause cancer. Some of the
carcinogenic hydrocarbons are given below CH
9 , 1 0 - D i m e t h y l -1 , 2 - b e n z a n t h r a c e n e

Uses of Benzene: industrial

solvent.

As an
[]
cleaning. alcohol.
1, 2-Benzanthracene [2] In dry of power and pestieid,
constituent

3] As a
manufacture
of a n
insecticide
e
[4] In the explosive.
ofan
manufacture

[5] In the of dyes.

manufacture

[6] In the of
manufacture
medicines.

[7] In the
ofperfumes.
manufacture

[8] In the of many

a r o m a t i c compounds,

In the synthesis
[9]
1,2-Benzpyrene [10] As a fuel

1,2,5,6-Dienzanthracene

124 Hydrocarbon