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Aromatic Hydrocarbons
Aromatic Hydrocarbons
Aromatic Hydrocarbons
Chapter-5
5. Aromatic Hydrocarbons
4.1. Definition: Aroma means characteristic odour. In early days of chemistry compounds
like benzaldehyde, toluene and benzene are known as aromatic compounds. Since all they
have characteristic odour and occur naturally. Benzaldehyde in cherries, peaches, and
almonds, Toluene in Tolu balsam, and benzene in coal tar. We now use the word aromatic to
refer to the class of compounds that contain six-membered benzene-like rings with three
double bonds. Thus, one of the parent structures in organic compound is benzene ring and any
compound containing benzene ring is called but do not having other elements than C and H
are called aromatic hydrocarbons.
O H CH3
C
Biphenyl Toluene
Benzene Naphthalene Antharacene Indene
.
4.2. Names of Aromatic compounds: Some common names of aromatic
compounds are given below.
O H CH3
C OH NH2 COOH
CaO
Heat
Zn Dust
+ ZnO
Heat
Benzene
. Phenol
5.3. Physical properties of benzene
1. Benzene is colourless liquid at room temperature.
2. Its boiling point is 80˚C.
3. It is insoluble in water.
4. It is soluble in most of the organic solvents, such as alcohol, ether, chloroform.
5. Benzene vapours are highly toxic which on inhalation lead to unconsciousness.
6. Benzene is well known carcinogen.
5.3. Reactions of Benzene:
Electrophilic substitution reactions: The The most common reaction of aromatic
compounds is electrophilic aromatic substitution, in which an electrophile (E) reacts with an
aromatic ring and substitutes for one of the hydrogens. Benzene shows electrophilic
substitution reactions, in which one or more hydrogen atoms of benzene ring are replaced by
electrophilic groups like -Cl, -Br, -NO2 , -SO3H, -R (alkyl group) , -COR, etc.
H E
E+ - is Electrophile H E
H H H H H H
+ Suitable solvent Fast
+ E
H H Reaction Conditions H H H H
H Slow H H
.
Benzene
Benzene undergoes electrophilic substitution reaction due to –
i. Resonance Stabilization of benzene ring
ii. Availability of loosely bound pi electrons for reaction.
5.3.1 Nitration: When benzene is heated with nitrating mixture i.e. mixture of concentrated
nitric acid and concentrated sulfuric acid at about 40 to 50 ˚C, it gives nitrobenzene.
The nitrating mixture generate electrophile +NO2 by reaction between HNO3 and H2SO4. The
reaction is given below.
HNO3 HO NO2
H2SO4 H OSO3H
5.3.2 Halognation: In this reaction, one of the hydrogen atom of benzene ring is replaced
by halogen atom.
H
X
Reaction
+ X2
Condition
Benzne Halobenzne
.
a. Formation of Chlorobenzene: Benzene reacts with chlorine gas, in dark in the
presence of iron or ferric chloride or anhydrous aluminium trichloride or red
phosphorous as catalyst to give chlorobenzene. Electrophile is Cl+ which is formed by
reaction between Cl2 gas and catalyst.
Cl Cl
Cl Cl Fe Cl Cl+ Cl Fe Cl
Cl Cl
H Cl
H Cl
Dark H
+
+ Cl
FeCl3/AlCl3
H+
Benzne Intermediate Chlorobenzne
Carbonium ion
.
With excess of chlorine, benzene gives hexachlorobenzene.
H Cl
H H Cl Cl
+ Cl2 Excess AlCl3 + 6HCl
H H Cl Cl
H Cl
Benzne Hexachlorobenzne
.
5 | Page D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44
Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus
b. Formation of Bromobenzene: Benzene reacts with Br2 gas, in dark in the presence of
iron or ferric bromide as a catalyst to give bromobenzene. Electrophile is Br+ which is
formed by reaction between Br2 gas and catalyst.
Br Br
Br Br Fe Br Br+ Br Fe Br
Br Br
H Br
H Br
Dark H
+
+ Br
FeBr3
H+
Benzne Intermediate Bromobenzne
. Carbonium ion
H+
Benzne Intermediate Iodobenzne
+ + Carbonium ion 65%
I2 + CuCl2 2I + 2Cu
.
5.3.3 Sulfonation: When benzene is heated with fuming sulfuric acid (oleum) at 373 K, it
gives benzene sulfonic acid. Electrophile generated is +SO3H.
Formation of the Electrophile: SO3 + Conc. H2SO4 can generate electrophile +SO3H or
Oleum (fuming H2SO4) can generate electrophile +SO3H.
+
SO3 + H2SO4 SO3H + HSO4-
H SO3H SO3H
H
SO3 /H2SO4 H
+ SO3H
Or Oleum
H+
Benzne i.e. fuming H2SO4 Intermediate Benzne Sulfonic acid
. Carbonium ion
5.3.4 Friedel-Craft Alkylation: When benzene is treated with an alkyl halide like in
the presence of Lewis acid as a catalyst such as anhydrous aluminium chloride, then alkyl
substituted benzene is obtained as a product. AlCl3 is electron deficient species, hence it
withdraws -X group as X- from R-X (alkyl halide) to generate electrophile R+ i.e. carbonium
ion. Then in next step R+ react with benzene to from R substituted benzene as a product. This
is called as Friedel Craft Alkylation.
R X + AlCl3 R XAlCl3
H R
H R
H
R-X + AlCl3
+ R+
H+
Benzne Intermediate Alkylbenzne
Carbonium ion .
1) H3C Cl + AlCl3 CH3 + ClAlCl3
H
H CH3 CH3
H
CH3Cl + AlCl3
+ +
+ CH3
H+
Benzene Intermediate Toluene or
Carbonium ion methyl benzene
2) C2H5 Cl + AlCl3 C2H5 + ClAlCl3
H
H C2H5 C2H5
H
C2H5Cl +AlCl3
+
+ C2H5
H+
Benzene Intermediate Ethylbenzne
Carbonium ion .
i. Aryl halides and vinylic halides don’t react because aryl and vinylic carbocations are too
high in energy to form under Friedel–Crafts conditions.
ii. Multiple products can be obtained in a reaction. Since it is difficult to stop the reaction at
single substitution.
.
iii. Rearranged product can be obtained in a reaction.
5.3.5 Friedel-Craft Acylation: When benzene is heated with an acyl halide or acid
anhydride in the presence of Lewis acid catalyst such as anhydrous aluminium chloride, then
corresponding acyl benzene is formed. This is called as Friedel Craft Acylation.
O O
+ AlCl3 C + AlCl4
1) H C C Cl H3C
3
O O CH3
H C CH3
H C
O
CH3COCl + AlCl3 H
+ C
CH3 H+
Benzene Intermediate Actophenone
Carbonium ion
H
O CH3
O
C
AlCl3 O
2) + C CH3
O
+ H3C C OH
Benzene C CH3
O
Actophenone
.
+ KMnO4
H2O
H2O
+ KMnO4
Co(III)
+ O2
COOH
CH3
Terephthalic acid
p-xylene .
Condition for side chain oxidation: For side chain oxidation, carbon next benzene ring must
contain-H atom (benzylic hydrogens) otherwise oxidation reaction do not take place. Since at
the position intermediate benzylic is formed. Thus, as tert-butylbenzene has no benzylic
hydrogens, it does not undergo oxidation with KMnO4/H2O.
CH3
H3C C CH3
KMnO4
No Reaction
H2O
t-butylbenzene
.