Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

Chapter-5

5. Aromatic Hydrocarbons

University syllabus: [5 L] Introduction and IUPAC nomenclature, preparation (Case benzene):

from phenol, by decarboxylation, from acetylene, from benzene sulphonic acid. Reactions (Case
benzene): Electrophilic substitution: nitration, halogenation and sulphonation. Friedel-Craft’s
reaction (alkylation and acylation) (up to 4 carbons on benzene). Side chain oxidation of alkyl
benzenes (up to 4 carbons on benzene).

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

Benzene Benzaldehyde Toluene

.
The major natural source of organic compounds is coal tar. When distillation of coal
tar is done in absence of air many aromatic hydrocarbons are distilled out. These are benzene,
toluene, naphthalene, biphenyl, anthracene, Indene, etc.
CH3

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

Benzene Benzaldehyde Toluene Phenol Aniline Benzoic acid

.

Naphthalene Antharacene Indene Biphenyl Phenanthrene

.
2 | Page D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44
Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

5.2. Methods of synthesis:

Industrial source of aromatic compounds Coal tar and petroleum are major sources of
aromatic compounds. In Laboratory they an be synthesized by one of the following methods.
5.2.1 From acetylene: Acetylene when passed through a red hot iron tube at 600 ˚C, then
acetylene polymerize to form benzene.
H H H
C C H H
Red Hot
C C
Iron Tube H H
H H
H C C H H
Acetylene Benzene
.
5.2.2 From Sodium Benzoate by decarboxylation: When anhydrous sodium
benzoate is heated with soda-lime it gives benzene.
COONa

CaO
Heat

Sodium Benzoate Benzene

.
5.2.3. From phenol (By reduction): Benzene is formed when vapours of phenol are
passed over heated zinc dust.
OH

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.

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Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

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.

From the diagram it is clear that pi bonding

orbitals of benzene rind are perpendicular to
benzene ring. The orbital overlap is from
upper and lower side of benzene ring. Thus,
electron density of pi bonds is above and
lower side of benzene ring.
Pi-bonding orbitals in benzene
The pi bonding electrons can be easily used for chemical reaction as they are loosely
bound. Thus, electrophile can easily attack on pi electrons of benzene ring. The attack of
electrophile on benzene ring generate carbonium ion at adjutant C atom. This disturb
aromatic character of benzene ring. However, carbonium ion is stabilised by resonance
effect. Due to aromatic nature benzene ring is highly stable. Thus, in second step carbonium
ion undergoes de-protonation so as to gain stable aromatic ring structure again.
In second step carbonium ion can gain nucleophile and form addition product. In addition,
product one double bond is removed that loss the aromaticity i.e. stability of benzene ring.
Thus, benzene undergoes, nucleophilic substitution reaction.
E
H E
H H H H
Deprotonation
H
H H H H
H H
+ E+ H Stable
H
H H
H E
H H E
Benzene
H H
x- H
H
Addition
X
H H
H H
H
H Less stable
.

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.

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Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

HNO3 HO NO2

H2SO4 H OSO3H

O2N + H2O + HSO4-

HO
O2N + H OSO3H
electrophile
H2O produced in reaction is protonated immediatly
H2O + H2SO4 H3O+ + HSO4-
.
+
The nitronium ion ( NO2) act as a electrophile. It reacts with benzene to from
nitrobenzene as a product of electrophilic substitution reaction.
H NO2 NO2
H
H
HNO3
+ NO2
H2SO4
Benzne 50 oC Intermediate H+ Nitrobenzne
Carbonium ion .

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

c) Formation of Iodobenzene: Iodine itself is unreactive toward aromatic rings. In presence

of oxidizing agent such as hydrogen peroxide or a copper salt such as CuCl2 then
iodination take place.
H I
H I
I2 + CuCl2 H
+
+ I

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.

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Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

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 .

Limitations of Friedel-Craft Alkylation:

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Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

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
.

8 | Page D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44

Inorganic Organic Chemistry Paper-II SPPU 2020 Revised Syllabus

5.4 Side Chain Oxidation an alkylated Benzene:

Benzene ring is unsaturated. Though it is unsaturated it isinert to strong oxidizing
agents such as KMnO4 and Na2Cr2O7, reagents that oxidize C=C in alkene. The presence of
the aromatic ring shows a dramatic effect on reactivity of alkyl side chains. Alkyl side chains
react rapidly with oxidizing agents and are converted into carboxyl groups -CO2H. The net
effect is conversion of an alkylbenzene into a benzoic acid, Ar-R to Ar-CO2H. Butylbenzene
is oxidized by aqueous KMnO4 to give benzoic acid, for example.
CH2CH2CH2CH3 COOH

+ KMnO4
H2O

n-butylbenzene Benzoic Acid

.
Toluene and p-methyl toluene (p-xylene) can be oxidized to benzoic acid and p-
dibenzoic acid i.e. terephthalic acid respectively by KMnO4/H2O and O2/Co(III) catalyst.
Terephthalic acid is industrially important compound and it is prepared by oxidation of p-
xylene. Every year more than 20 million tons of terephthalic acid is produced by this method.
CH3
COOH

H2O
+ KMnO4

Toluene Benzoic Acid

COOH
CH3

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
.

9 | Page D. R. Shinde, Dept. of Chemistry, RMACS College, Akurdi, Pune-44