Aromatic

Hydrocarbon
By: Vishal Thapa
United Academy
2
Syllabus
Class-XII
1. Aromatic Hydrocarbon
• Definition, characteristics of aromatic compounds, Huckel’s rule
• Nomenclature of aromatic compound, Isomerism
• Structure of benzene
• Orientation of benzene derivatives
• Preparation of Benzene from
i. Decarboxylation ii. Phenol iii. Ethyne iv. Chlorobenzene
• Physical properties of benzene
• Chemical properties of benzene
i. Addition reaction: Hydrogen, halogen and ozone
ii. Electrophilic substitution reactions: Nitration, sulphonation,
halogenation, Friedel-Craft’s alkylation and acylation
iii. Combustion of benzene and Uses of benzene

3
 Aromatic Hydrocarbon ( Arene )
The term aromatic was derived from Greek word ‘Aroma’ which means sweet smell. Benzene
and its derivatives are called aromatic compound because of their aroma odour.
The modern definition of the term aromatic compounds is based on the structure rather than
‘aroma’ odour. Thus, those cyclic hydrocarbon, which have alternate C-C and C=C bonds and
similar to benzene ring in characters are known as Aromatic hydrocarbon. These are also known
as Arenes.
For example:

Benzene Naphthalene Anthracene

4
 Characteristics of aromatic compounds
1. Aromatic compounds should be cyclic, planar (each ring
forming atoms should be sp2 hybridized) so that p-orbitals
is available for continuous delocalization of π-electrons.

2. They are highly unsaturated but do not give addition

reactions. Instead they give electrophilic substitution
reactions.
3. They should have higher % of carbon than the
corresponding aliphatic compound. Hence, they burns with
sooty flame.

4. For the compound to be an aromatic, it should follow the

Huckel’s Rule i.e. ( 4n + 2 ) π-electrons.
5
 1. Aromatic
compounds should
be cyclic, planar
Benzene
(each ring forming
atoms should be sp2
hybridized) so that
p-orbitals is
available for
continuous
delocalization of π-
electrons.

6
 Three double bond so
2. They are highly unsaturated
highly
unsaturated but
Addition reaction
do not give CCl4
CH2 =CH2 + HCl CH3 -CH2-Cl
addition
But,
reactions.
Instead they + HCl No reaction

give
electrophilic Electrophilic substitution reaction Cl
substitution
AnhydrousAlCl3
+ HCl
reactions. + Cl2
cold, dark

7
 Aliphatic compound
Alkane (CnH2n+2)
3. They should Hexane=C6H14, % of C= 30%
have higher %
of carbon than Alkene (CnH2n)
the Hexene=C6H12, % of C= 33.33%
Hexa-1,3,5-triene= C6H8, % of C= 42.85%
corresponding
aliphatic Alkene (CnH2n-2)
Hexyne=C6H10, % of C= 37.5%
compound.
Hence, they
Aromatic compound
burns with
sooty flame. Benzene=C6H6, % of C= 50%

8
 Huckel’s Rule
It states that, “ All those cyclic compound that
4. For the contains a delocalized system of ( 4n + 2 ) π-
electrons which is uniformly spread through out the
compound to whole ring are aromatic, where n= 0, 1,2,3……
(integers) i.e. 2,6,10,14,18π-electrons’’ .
be an For example: Benzene
In benzene,
aromatic, it Total numbers of delocalized π-electrons = 6π
should follow electrons
According to Huckel’s rule i.e. ( 4n + 2 ) π-electrons
the Huckel’s ,
when n=1, number of delocalized π-electrons = 4 x
Rule i.e. 1 + 2 = 6π
Thus, Benzene obeys Huckel’s rule.
( 4n + 2 )
π-electrons. Benzene

Why is benzene called aromatic compound

according to Huckel’s Rule? 9
 Aromaticity
Or
What are the criteria to be an aromatic
compounds?
For a compound to be an aromatic, it should have the
following criteria:
i. Compound must be cyclic.
ii. Compound must be planar. (each ring forming atoms
should be sp2 hybridized )
iii.There must be cyclic resonance in ring.
( continuous delocalization of π-electrons )
iv. It must follow Huckel’s Rule i.e. ( 4n + 2 ) π-electrons.
10
❑ Examples of aromatic compounds obeying Huckel’s rule:
Value ( 4n + 2 ) π- Structure and name of aromatic compound
of n electrons
0 4 x 0 + 2=2 + H
c +

c c
Cyclopropenyl cation H H
1 4 x 1 + 2=6

.. ..
Benzene .. ..
Thiopene
..
Pyridine Pyrrole Furan
2 4 x 2 + 2=10

Naphthalene
3 4 x 3 + 2=14

Phenanthrene
11
Anthracene
❑Nomenclature of aromatic compound
1. Naming of mono-substituted benzene
Monosubstituted benzenes are usually named by prefixing the name of the
substituent before the word ‘benzene’. Example:
Cl Br NO2 CH2CH3

Chlorobenzene Bromobenzene Nitrobenzene Ethylbenzene

However, some of the monosubstituted benzenes are known by their special
names

OH NH2 CH3

Hydroxybenzene Aminobenzene Methylbenzene

(Phenol) (Aniline) (Toluene)
12
 CHO OCH3 COOH

Benzaldehyde Methoxybenzene Benzoic acid

(Anisole)

2. Naming of disubstituted benzene [ Isomerism ]

A disubstituted benzene shows isomerism (i.e. position isomerism ). The second
substituent can enter into any one of the five positions of the ring. Since positions
( 2 and 6 ) and ( 3 and 5 ) are equivalent positions, there can be three isomers of
the disubstituted benzenes. Example:
Cl
Cl Cl Cl Cl 1
2
1
2 Cl Cl 2 1 1
2 2
1
2
6
3 3
3
5 3 4
3 Cl Cl
4 Cl
1,4-dichlorobenzene
1,2-dichlorobenzene 1,3-dichlorobenzene
13
 X X OMG
1 OMP
ortho 6 2 ortho O O

meta 5 3 meta m m
4 p
para
Example: CH3
CH3 CH3
CH3

CH3 CH3
1,2-dimethylbenzene 1,3-dimethylbenzene 1,4-dimethylbenzene
or or or
(o - dimethylbenzene) (m-dimethylbenzene) (p - dimethylbenzene)
or or or
(o-xylene) (m-xylene) (p-xylene)
14
 Br
Br Br
Br

Br Br
1,2-dibromobenzene 1,3-dibromobenzene
or or 1,4- dibromobenzene
(o - dibromobenzene) (m- dibromobenzene) or
(p- dibromobenzene)
If two different substituents are present then, ortho, meta and para is
followed by the substituent in an alphabetical order. Cl
Example: 1
NO2 Cl 2
3
2 Cl 2
1 3
1 4
Br CH2CH3
1-bromo-3-chlorobenzene 1-chloro-4-ethylbenzene
1-chloro-2-nitrobenzene
or or
or
(m- bromochlorobenzene) (p- chloroethylbenzene)
(o - chloronitrobenzene) 15
If one of the substituent present in the
disubstituted benzene gives the special name,
then disubstituted benzene is named as
derivatives of that special molecules.
Example:

Cl 3
OH
H3 C 2
2 4 I
1
1
HO
Toluene (Phenol)
2-chlorotoluene 4-iodophenol
or or
(o - chlorotoluene) (p - iodophenol)

16
If both the substituent present in disubstituted benzene give
the special name, then the substituent with higher priority is
numbered as 1.

17
 NH2
CHO 4
1 OH 2 OH 3
2

1 COOH 2
1

2-hydroxybenzaldehyde 2-hydroxybenzoic acid OH

or or
4-aminophenol
(o - hydroxybenzaldehyde) (o - hydroxybenzoic acid)
or
or or
(p - aminophenol)
(salicylaldehyde) (salicylic acid)

CH3
2 OH
1

2-methylphenol
or
(o - methylphenol)
or
(o-cresol)
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 Br NH2 OH
1 1 1
6 2 Cl 2 Cl O2N 6 NO2
6 2
5 3 3
5 5 3
Br 4 Br 4 4
1,3,5-tribromobenzene
Cl NO2
2,4,6-trichloroaniline
2,4,6-trinitrophenol
(picric acid)

CH3 In some cases benzene ring is considered as

1 substituent.
O2N 2 NO2 Example:
6

5 3
4 CH CH OH
2 21 2
NO2
2,4,6-trinitrotoluene CH CH COOH
(TNT) 3 2 1
(phenyl) (3-phenylprop-2-enoic acid)
(2-phenylethanol)
Cinnamic acid
19
❑Benzyl, Benzal and Benzo groups
Group Example
CH3
CH2 CH2 Cl
Methylbenzene
Benzyl Benzyl chloride
(Chlorophenylmethane)

Cl
CH CH or CHCl2
Cl
Benzal Benzal chloride or Benzal dichloride
(Dichlorophenylmethane)

Cl
C C Cl or CCl3
Cl
Benzo
Benzo chloride or Benzo trichloride 20
(Trichlorophenylmethane)
❑Structure of Benzene
1. Kekule’s structure of Benzene

2. Molecular orbital structure of Benzene

3. Resonance structure of Benzene

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 ❑Structure of Benzene
1. Kekule’s structure of Benzene Friedrich August Kekule von Stradonitz
In 1865, August kekule suggested a cyclic, planar structure of benzene which
consists of a regular hexagon in which carbon atoms are linked together by an
alternative system of single and double bonds.

or

Benzene
▪ Objection to the Kekule's structure
The Kekule’s structure predict two isomers of 1,2-dibromobenzene as given
below:

(II)
(I) 22
 In structure I, double bond separates the two bromine atoms and in structure II, a single
bond separates the two bromine atoms. But there exists only one ortho-disubstituted
benzene. To explain this, kekule suggested that double bonds and single bonds in benzene
exchange their position very rapidly and the dynamic equilibrium between structure (A)
and (B) is maintained.

(A) (B)
1.39 A0
Fig: Kekule’s structure of Benzene
From the bond length measurement by X-ray diffraction studies, the C-C bond length in
benzene is found to be equal to 1.39 A0 which is intermediate bond length between C-C
single bond length (1.54 A0) and C=C double bond length (1.34 A0). This means all the C-C
bonds in benzene are equivalent. This will be true only when benzene exists as a hybrid of
two resonance structure.

or

….
….
1.09 A0
Resonance structure Resonance hybrid 23
2. Molecular orbital structure of Benzene
Before starting the molecular orbital structure of Benzene
Z
X

Spherical shape
Y

Fig: s-orbital

Dumbbell shape

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 + +
s-orbital
p-orbital 2 sp hybrid orbital

+ + + +
s-orbital
p-orbital p-orbital 3 sp2 hybrid orbital

+ + + + + +
s-orbital
p-orbital p-orbital p-orbital 4 sp3 hybrid orbital
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 1800C
+
sp sp

2 sp hybrid orbital
Linear structure

26
 sp2

1200
+ +
sp2 sp2
3 sp2 hybrid orbital Trigonal planar structure

27
 109028’

+ + +

4 sp3 hybrid orbital

Tetrahedral structure

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sp2-hybridization
The process of hybridization in which one s-orbital
intermixes with two p-orbitals of nearly equal energy
to form three hybrid orbital is called sp2-hybridization.
sp2

1200
+ +

sp2 sp2
l

sp2-hybridization

29
i. Ethylene or Ethene ( C2H2 or CH2= CH2 )
In ethylene, carbon undergoes sp2-hybridization. Here,
carbon atom forms three σ bond by using three hybrid orbitals.
Example: CH2= CH2
C 1S2 2S2 2P2 Energy of orbital= n+ l
Ground state
n= Principal quantum number
2S l= Azimuthal quantum number
2P
Excited
Value of l for
state 2Px 2Py 2Pz s=0
p=1
d=2
Hybrid orbital of same energy
sp2 sp2 sp2
f=3
2Pz orbital H
H
sp2 C=C
H H
C sp2-hybrid orbital Ethene

sp2 30
 Out of three sp2-hybrid orbitals of carbon two hybrid orbitals are
used to form σ bond with 1s orbital of two hydrogen and one hybrid
orbital is used to form σ bond with sp2-hybrid orbitals of another
carbon. The unhybridized 2Pz orbitals of carbon-atom undergo side
to side overlap to form a π- bond.
2Pz 2Pz
π- bond
H
H
sp2 sp2 H H
σ bond π- bond
σ bond Cσ bond C
C sp2 sp2 C
σ bond σ bond H 1200 H
sp2 sp2

σ bond H
H

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Benzene
H H
C C
C 6 H6 H C
C C
C H

H H

6 C 6 H

32
 Molecular orbital structure of Benzene
H
H
C C

C H
H C

C C

H H
33
 H H

c c

H c c H
Fig: Sidewise overlap of
c c unhybridized p-orbitals
H
H to form π-bonds

H H
C C
H C C H
C C
H H
Fig: π- electrons cloud lying above and below the plane34
3. Resonance structure of Benzene
❑ Orientation in Benzene
The arrangement of the substituents on the benzene
ring is termed as orientation. This term is used for
determining the position of the substituents on the
benzene ring. The nature of group already present on
the benzene ring decides the position of newly
coming substituents. On the basis of their directing
influence, the groups are classified into following
two groups;
1)Ortho- para directing group or o/p- director
2)Meta directing group or m- director
35
1. Ortho- para directing groups or o/p-
directors
The group already present on the benzene ring
which directs the newly coming electrophile towards
ortho or para position to it is called ortho-para
directors.
o/p directing groups are the groups in which the
central atom should have at least one lone pair of
electrons and bonded with other atoms by single
covalent bonds or it may be electron releasing group.

Example: -Cl , -OH, -NH2, -OR etc

36
 ❖Ortho- para directing compounds
.. .. ..

..
..

..
O-R

..
NH2
..
Cl OH

Chlorobenzene Phenol Aniline Alkoxybenzene

Central atom-Cl Central atom-O Central atom-N Central atom-O

No. of lp=3 No. of lp=2 No. of lp=1 No. of lp=2

Central atom- Directly attached to benzene ring

Example
Cl Cl Cl
NO2
+ Conc. HNO3 + H2O
+ NO2 +
Conc. H2SO4
Chlorobenzene
NO2 37
Q. Why does Chlorobenzene undergoes electrophilic substitution reaction at
o/p position?
.. ..
Ans: This can be explained by resonating structure of Chlorobenzene as follows:
.. + Cl + Cl

..
..
..
Cl ..

(II) (III)
(I) Resonance structure
.. ..
δ+ Cl
..
.. Cl
+ Cl

..
δ- δ-
≡
δ- (V)
Resonance Hybrid (IV)
In the above resonance structure II,III and IV, the electron density is relatively higher at
the ortho and para position than at meta positions. Thus, the newly coming electrophile
prefer to attack at ortho and para positions. 38
Q. Why does Phenol undergoes electrophilic substitution reaction at o/p position?
Ans: This can be explained by resonating structure of phenol as follows:
.. .. ..
+ OH + OH
..
OH

(I) (II) (III)

Resonance structure
δ+ OH .. ..
.. OH + OH
δ- δ-
≡
δ- (V)
Resonance Hybrid (IV)
In the above resonance structure II,III and IV, the electron density is relatively higher at the
ortho and para position than at meta positions. Thus, the newly coming electrophile prefer to
attack at ortho and para positions. 39
Class work
Q. Why does aniline undergoes electrophilic
substitution reaction at o/p position?

40
 + NH2 + NH2
..
NH2

(I) (II) (III)

Resonance structure

δ+ NH2 .. NH2 + NH2

δ- δ-
≡
δ - Hybrid
Resonance (V)
(IV)
In the above resonance structure II,III and IV, the electron density is relatively higher at the
ortho and para position than at meta positions. Thus, the newly coming electrophile prefer to
attack at ortho and para positions. 41