Prof.

Muhammad Ahmed 0323-4054130

Aromatic Hydrocarbons Arenes

Aromatic word come from Greek word Aroma = fragrance

Benzenoid aromatic compounds. Tolune,aniline,phenol

Aromatic compounds
Unbenzenoid aromatic compounds. Furan,pyrrol,

Types of Aromatic compounds

Monocyclic Aromatic compounds Polycyclic Aromatic compounds

CH3
CHO

Isolated
Toluene Benzaldehyde
Biphenyl

NH2

SO3H CH2

Diphenyl methane

Aniline Benzene sulphonic acid

Cl
Fused
OH C4r + 2.H2r+4

C10H8
Naphtalene
Chlorobenzene Phenol

NO2
COOH C14H10

Anthracene

Nitrobenzene Benzoic acid

CH2-OH
CH = CH2
C14H10

Phenanthrene
Benzyl alcohol styrene or vinyl benzene
Prof.Muhammad Ahmed 0323-4054130

Number of sigma and pi bonds in Benzene 12 sigma bonds and 3 pi bonds.

Number of sigma and pi bonds in Naphthalene 19 sigma and 5pi bonds.

Phenyl and Aryl group

Phenyl group is a type of aryl group. Aryl groups are functional groups present in organic compounds
that are aromatic. Aryl group always contains an aromatic ring. Phenyl is the chemical structure derive
from a benzene ring

C6H5 -

Phenyl group

Ph -

Y CH3

Aryl group
Prof.Muhammad Ahmed 0323-4054130

Nomenclature of Aromatic compounds

(1) Monosubstituted Benzene

Monosubstituted derivatives of benzene are named systematically using benzene as the parent and listing the
substituent as a prefix.

CH3
NH2
CHO

Toluene Benzaldehyde Aniline

Methylbenzene Aminobenzene
Formylbenzene

NO2
Cl
SO3H

Benzene sulphonic acid Nitrobenzene

Chlorobenzene

CH2-OH
OH
COOH

Benzyl alcohol Phenol

Hydroxybenzene Benzoic acid
Carboxylicbenzene

CN
OCH3
CH = CH2

Anisole
Phenylbenzene Cyanobenzen Methoxybenzene styrene or vinyl benzene
Prof.Muhammad Ahmed 0323-4054130

(2) Disubstituted Benzene When Both sustituents are same

1
Ortho = o = 1 2
2 2

meta = m = 1 3
3 3
para = p = 1 4
4

When both substituents are same then give priority to any one and then give lowest
number to 2nd same substituent

There are three monosubstituted isomeres ( Positon isomers )

Isomers of xylene:
CH3 CH3 CH3

CH3

CH3
CH3
1,2-Dimethylbenzene 1,3-Dimethylbenzene 1,4-Dimethylbenzene
o - xylene m - xylene p - xylene

Isomers of Cresol:

Isomers of Dihydroxybenzene
Prof.Muhammad Ahmed 0323-4054130

(2)Disubstituted Benzene When both substituents are different

When two or more different substituents are present then give the one substiiuent priority
from the priority list (give parent name) then rest of substituents are given lowest possible
number according to base substituent position one.

Priority list:

-COOH > -CN > -CHO > -COR > -OH > -NH2 > -OR > -R

CAR CYN CHO KOHE NHHOR R

CH3 OH CHO COOH NH2 OCH3

Toluene Phenol Benzaldehyde Benzoic acid Aniline Anisole

CN

CH3

COOH

OH

NH2

OH
Prof.Muhammad Ahmed 0323-4054130

NH2

OCH3

CH3

Br

C 2H 5

CN

Cl

Br

NO2

I
Prof.Muhammad Ahmed 0323-4054130

Draw structure of the following compounds

2 - Hydroxytoluene

m - ethylcyanobenzene

3 - Cyanophenol

4 - Iodonitrobenzene

2,4 - Dinitrotoluene
Prof.Muhammad Ahmed 0323-4054130

Dest.dist.
M.Faraday (1825) : Vegetabel oil Benzene
Discovery of Benzene
fract.dist.
Hoffmann ( 1845) Coal tarr Benzene

ari
s
An
ed
m
Ah 30 re
d
a 541 o
m 0 Lah
m
a 3- 4
uh 032 ege
l
f.M Col
o
Pr jab
n
Pu
Prof.Muhammad Ahmed 0323-4054130
Prof.Muhammad Ahmed 0323-4054130

Properties of Benzene Before its structural determination Straight chain structure of benzene are ruled out

HC = CH-CH2-CH2-C = CH H2C=CH-C = C - CH = CH2

1) Empirical formula of benzene determine by combustion analysis = CH Empirical formula = CH

2) Molecular mass of benzene by Vapour density method = 78 Molecular mass = 78

3) Molecular formula of benzene is = C6H6 Molecular formula = C6H6

4) Molecular formula show it is highly unsaturated Molecular formula show it is highly unsaturated

5) Benzene show saturated behaviour( Break sigma bond ) why it show saturated behaviour

Not reated with KMnO4 why it does not reaction with KMnO4
Why give substitution reaction instead of additon
Give substitution reaction with HNO3 and H2SO4
These structure show unsaturated behaviour
6) Benzene show unsaturated behvaiour( Break pi-bond)
Give addition reaction with H2 ( 4H2 added in one straight molecule)
Give addItion reactin with H2( 3H2 molecules added in one benzene)
Give addition reaction with X2 ( 4X2 added in one straight molecule)
Give addition reaction with X2( 3X2 molecules added in one benzene)

7) Benzene has only when monosubstituted isomer These structure has more than one monosubstituted isomers
8) Benzene has three disubstituted isomers These structure has more than three disubstituted isomers
Benzene dose not show general formula with
Alkane CnH2n + 2
Alkene CnH2n C6H14
Alkyne CnH2n -2 C6H12
C6H10

OH OH OH OH OH OH

H2C=CH-C = C - CH = CH2 + KMnO4 H2C - CH - C - C - CH - CH2

OH OH

X X
HC = C - CH2 - CH2 - C = CH HC = CH-C = C - CH = CH2

X X
HC = CH - CH2 - CH2 -C = CH H2C=CH - C = C - CH = CH2

X X X X
HC = CH-CH2-CH2-C = CH HC = CH-CH2-CH2-C = CH

X X X
HC = CH-CH2-CH2-C = CH HC = CH-CH2-CH2-C = CH

X
Prof.Muhammad Ahmed 0323-4054130

Kekule 's Structure of Benzene 1865

According to Kekule benzene is:

Cyclic regular hexagonal planar strucuture
Benzene has three alternating double bonds

Give addition reaction with H2. Three molecules of H2 added in one molecule of benzene.

Pt
+ 3H2

Give addition reaction with X2. Three molecules of X2 added in one molecule of benzene.
Cl

sunlight Cl Cl
+ 3Cl2
Cl Cl

Cl

Like benzene it kekul structure has only one monosubstituted isomer

X

+ X

Like benzene kekule has only three disubstituted isomers

X X X X

Y
+ Y + +
Y

Y
Objection in Kekul structure of benzene:
(1) Why it does not react with KMnO4
(2) Why benzene give substitution reaction easily as compare to addition reaction
Why benzene break sigma bond easily as compare to pi-bond

(3)How benzene has cyclic regular hexagonal planer structure

(4) Why benzene is too much stable.
Prof.Muhammad Ahmed 0323-4054130

X - Ray Analysis of Benzene

When analysis of benzene is done by the x-ray diffraction method, it also gives information related to the
structure of the benzene. By using the x-ray diffraction method, it confirms the hexagonal structure of the
benzene. It also shows the hexagonal ring in one plane.

i
sar
An
ed
m
Ah 30 e
ad 541 hor
m
m -40 La
a 3 g e
uh 032 lle
M
r of
. Co
P ab
unj
P
Prof.Muhammad Ahmed 0323-4054130
Prof.Muhammad Ahmed 0323-4054130

Atomic Orbital Treatment of Benzene

Localized pi - bond Delocalized pi-bond

Less stable Most stable

Have high energy Have low energy
just res.contributor structure Real structure
never exist Actual/hybrid structure
Prof.Muhammad Ahmed 0323-4054130

The Benzene is extraordinary stabel due to delocalization of π - electrons

Stability of benzene is determine by heat of hydrogenation

The Stability of Benzene
Heat of hyrdogenation of one mole of C = C double bond is = -119.5kj/mole

Hydrogenation of Cyclohexene

+ H2 Pt ▲H = - 119.5 kj/mole

Cyclohexene Cyclohexane

Expected ▲H = -119.5 kj/mole

Observed ▲H = - 119.5 kj/mole

Hydrogenation of 1,3-Cyclohexadiene

2
Pt
+ 2H2 ▲H = -231.5 kj/mole
3

4
Cyclohexane
1,3-Cyclohexadiene

Expected ▲H = 2 ×( -119.5) = - 239 kj/mole

Observed ▲H = - 231.5 kj/mole

Hydrogenation of 1,3,5-Cyclohexatriene

1
e
ur
ct

6 2 Pt
ru

+ 3H2 ▲H = - 358.5kj/mole
st
al
ic

5 3
et
th
po

4
Cyclohexane
Hy

1,3,5-Cyclohexatriene

Expected ▲H = 3 ×( -119.5) = -358.5 kj/mole

Observed ▲H = - 208 kj/mole

Difference = R.E = +150.5kj/mole

Pt
+ 3H2 ▲H = -208kj/mole

Benzene Cyclohexane
Prof.Muhammad Ahmed 0323-4054130

The energy difference between resonance contributing structure and

hybrid structure called resonance energy.
Resonance Energy
Resonance energy of Benzene = +150.5kj/mole

Resonance energy × stability of compound

Prof.Muhammad Ahmed 0323-4054130

The possibilities of different pairing scheme of valence electron of

Resonance or Conjugation atom to form different structures called resonance and structures
called resonance contributing structure.

kekule structures Dewar structures

C - C in alkane 1.54Ao

C = C in alkene 1.34Ao

C = C in alkyne 1.20Ao

C - C in benzene 1.397Ao
Prof.Muhammad Ahmed 0323-4054130

Preparation of Benzene and its Derivative

From Cycloalkane

Pd
250°C + 3H2

H H

H H
H

From n - Hexane

CH3 CH2 CH

CH2 CH3 Al2O3 + SiO2 + Cr2O3 CH CH

Al2O3 + SiO2 + Cr2O3 CH2 CH2
o
o 500 C
500 C
CH2 CH CH
CH2 CH2 CH2

CH2 CH
CH2

OR

n - CH3 - (CH2)4 - CH3

Al2O3 + SiO2 + Cr2O3
o
+ 4H2
500 C
Prof.Muhammad Ahmed 0323-4054130

From n - Heptane

CH3 CH3 CH3

CH2 CH C

CH2 CH3 Al2O3 + SiO2 + Cr2O3 CH CH

Al2O3 + SiO2 + Cr2O3 CH2 CH2
o
o 500 C
500 C
CH2 CH CH
CH2 CH2 CH2

CH2 CH
CH2

OR

CH3

n - CH3 - (CH2)5 - CH3

Al2O3 + SiO2 + Cr2O3
o
+ 4H2
500 C

n-Heptane
Toluene
Prof.Muhammad Ahmed 0323-4054130

Preparation in Lab

By Decarboxylation of Benzoic acid salt

COONa

CaO + Na2CO3
+ NaOH

Sodium benzoate

By Distill phenol with Zn

OH

+ Zn + ZnO

By Hydrolysis of Benzene suphonic acid

SO3H

HCl
+ H2O + H2SO4
boil
Prof.Muhammad Ahmed 0323-4054130

Wurtz - Fitting Reaction

ether
Ph - X + R - X + 2Na Ph - R + 2NaX
ether
Ph - X + Ph - X + 2Na Ph - Ph + 2NaX

Cl CH3

+ CH3 - Cl + 2Na ether

+ 2NaCl

Toluene

Br CH2-CH3

2Na + 2NaBr
+ CH3 -CH2 -Br
ether

Ethyl benzene

Wurtz - synthesis

ether
R - X + R - X + 2Na R - R + 2 NaBr

ether
H3C - Br + H3C - Br + 2Na H3C - CH3 + 2 NaBr
Prof.Muhammad Ahmed 0323-4054130

Electrophilic substitution reaction

Reaction of Benzene Addition reaction

Oxidation

Electrophilic Substitution Reactions

Halogenation
Nitration
Sulphonation
F.C.Alkylation
F.C.Acylation

General Mechanism of Electrophilic Substitution Reaction

H
E
+
+ E
Electrophile
+

H
E
E
+ BH
+ B
+

........................................OR.............................................

H
E
+
+ E +

H
E E
+ + B + BH
Prof.Muhammad Ahmed 0323-4054130

FeF3
Benzene + F2 Reaction vigorously

FeCl3
Benzene + Cl2 Normal reaction
(1) Halogenation
FeBr3
Benzene + Br2 Normal reaction

Benzene + I2 FeI3
poor yield

FeX3 or AlX3

X
Catalyst
+ X2 + HX

FeCl3 Cl
+ Cl2 + HCl

Chlorobenzene

Mechanism: + -
Cl - Cl + FeCl3 Cl + FeCl4

H
+ Cl+ Cl

H
Cl
+ FeCl4
- Cl
+ FeCl3 + HCl
+
Prof.Muhammad Ahmed 0323-4054130

+
The substitution of NO2 group on benzene called nitration of benzene

1:1 mixture of HNO3 and H2SO4

(2) Nitration
Temperatute: 50 - 55oC

Electrophile = Nitronium ion ( NO2+)

Reaction:
NO2

H2SO4
+ HNO3 o
50 - 55 C
+ H 2O

Mechanism:

O O O O

=
=

+s -s
=

=
+
H-O-S-O-H + H-O-N N + O - S - OH + H2O

=
=

O O O O

+ -
H2SO4 + HNO3 NO2 + HSO4 + H2O

H
NO2
+ NO2+
+

H
NO2 NO2
+ HSO4 + H2SO4
+
Prof.Muhammad Ahmed 0323-4054130

The substitution of suphonic group - SO3H on benzene ring called sulphonation

(3) Sulphonation of benzene

Benzene + fuming or conc.H2SO4 Benzene sulphonic acid

SO3H
H2SO4
+ H2SO4
80 C
o
+ H 2O

Benzene sulphonic acid

SO3H
o
25 C
+ SO3

Mechanism:
+
H2SO4 + H2SO4 SO3 + HSO4 + H3O

O O
H

+ S S O

O O O

H
SO3
SO3
+ HSO4
+ H2SO4

SO3 + SO3H
H 3O H 2O
+ +
Prof.Muhammad Ahmed 0323-4054130

Substitution of alkyl (R-) and acyl group( - COR ) on benzene

(4)Friedel - Craft Reactions ring called F.C. reaction.

(A) Friedel - Craft Alkylation Substitution of Alkyl group ( - R) on benzene called F.C.Alkylation

H3C
AlCl3
+ H3C Cl + HCl

Mechanism:

CH3 -Cl + AlCl3 CH3+ + AlCl4-

CH3 -Cl + AlCl3 CH3+ + AlCl4-

H
CH3 CH3
+ AlCl4- + AlCl3 + HCl

........................................................................................................................................................

AlX3
+ R-X + HCl
Prof.Muhammad Ahmed 0323-4054130

(B) Friedel - Craft Alkylation Substitution of Acyl group ( - COR) on benzene called F.C.Acylation

O O

=
=
AlCl3 C - CH3
+ CH3 - C - Cl + HCl

Acetophenone

Mechanism:
O O
=

=
CH3 - C - Cl + AlCl3 CH3 - C+ + AlCl4-

O H O

=
=

C - CH3
+ +
C - CH3
+

HO O
=

=
C - CH3 C - CH3
+ AlCl4
+ + HCl + AlCl3

Acetophenone
........................................................................................................................................................

O
O
=

C - Cl
+ AlCl3 C
+ HCl

Benzophenone
Prof.Muhammad Ahmed 0323-4054130

Reaction in which π -bond involved

Addition Reactios of Benzene

Unsaturated Behaviou of Benzene

Hydrogenation:

Ni
+ H2
200°C

Halogenation:
Cl
Cl Cl
Sunlight
+ Cl2
Cl Cl
Cl

1,2,3,4,5,6-Hexachlorocyclohexane

Ozonolysis O

O O
+ O3 or C6H6O9
O
O O
O Benzene triozonide

O
Prof.Muhammad Ahmed 0323-4054130

Oxidation Reaction of Benzene

Combustion

Flame
+ O2 CO2 + H2O

Catalytic Oxidation

+ KMnO4 No reaction

V2O5 HC C
+ O2
450°C
O
HC C

O Maleic anhydride

O +s -s O
H - OH
+s
HC C HC C OH
-s
O + H 2O
HC C
HC C OH

O
O
Maleic acid
Prof.Muhammad Ahmed 0323-4054130

Ozonolysis

CHO
H 2O
3
CHO
Glyoxal

Benzene triozonide

K2Cr2O7 + H2SO4
Side chain oxidation Oxidizing agents
KMnO4 + H2SO4

R COOH

H2SO4
+ KMnO4

CH3 COOH

H2SO4
+ KMnO4

CH2-CH3 COOH

H2SO4
+ K2Cr2O7

How to distinguish between benzene and toluene?

H2SO4
+ KMnO4 No reaction

CH3 COOH

H2SO4
+ KMnO4
Prof.Muhammad Ahmed 0323-4054130

+
Cl
Cl
FeCl3
+ Cl2

+
H 3C CH3

AlCl3
+ H3C - Br

OH + OH
H 3C OH
o CH3
AlCl3
+ H3C - Br
p

CH3

CHO + CHO
H 3C

AlCl3
+ H3C - Br m
CH3

+ NH2 NH2
NH2 H 3C
o CH3
AlCl3
+ H3C - Br
p

CH3

NO2 +
H 3C NO2

AlCl3
+ H3C - Br
m CH3
Prof.Muhammad Ahmed 0323-4054130

Orientation in Electrophilic Substitution Reaction of Benzene

Ortho - para Directing groups

These are electron donating group which donate electron into benzene ring. It increase electron
density at ortho and para position which activate these position. So incoming electrophile come
to ortho and para position.

Examples: OH OCH3 NH2

-OH

-NH2

CH3 Br NHR
-NHR

-NR2

-OR

-X I Cl NR2

-R

+ + +
:OH OH OH OH :OH

Negative charge come at ortho and para position so electron density increases at
these two position. incoming electrophile come at ortho and para positions.
Prof.Muhammad Ahmed 0323-4054130

NO2+ Br
Br Br

H2SO4 NO2
+ HNO3 +
NO2

OH + OH
H 3C OH
o CH3
AlCl3
+ H3C - Br
p

CH3

OCH3 + OCH3 OCH3

H 3C

AlCl3 CH3
+ H3C - Br

CH3

Br+ NH2 NH2

NH2
o Br
FeBr3
+ Br - Br
p

Br
Prof.Muhammad Ahmed 0323-4054130

meta - Directing groups

These are electron withdrawing group which withdraw electron from benzene ring. It decreases
electron density at ortho and para position to deactivate these position. So incoming
electrophile come to meta position.

Examples:
O O

=
O

=
=
C-H C-R
C - OH

- COOH

- CHO

- COR N+R3 C=N O O

=
N
-N+R3

-CN

-NO2+
O

=
-SO3H C - OR
O
=

-COOR S -OH
=

O O O O O

C-OH C -OH C - OH C - OH C - OH

+ +

The positive charge come at ortho and para position so electron density decreases
at these two position. Result, the incoming electrophile come at meta positions.
Prof.Muhammad Ahmed 0323-4054130

+
COOH Cl
COOH

FeCl3
+ Cl2
Cl

+
CHO H 3C CHO

AlCl3
+ H3C - Br
CH3

NO2 +
H 3C NO2

AlCl3
+ H3C - Br
CH3

+ SO3H
SO3H H 3C

AlCl3
+ H3C - Br m
CH3

+ CN
CN H 3C

AlCl3
+ H3C - Br
CH3

COCH3 H 3C
+
COCH3

AlCl3
+ H3C - Br
m CH3
Prof.Muhammad Ahmed 0323-4054130

Reactivity Order

Alkene > Alkyne > Benzene > Alkane

Prof.Muhammad Ahmed 0323-4054130
Prof.Muhammad Ahmed 0323-4054130