Aromatic Hydrocarbons: (Aroma or pleasant smell) These hydrocarbons are also known as arenes.
Aromatic compounds containing benzene ring known as benzenoids and those not containing benzene ring
are known as non – benzenoids.
CH3
Benzene Naphthalene Toulene Biphenyl
Nomenclature and isomerism: when two hydrogen atoms are replaced by two similar or different
monovalent atoms or groups three different position isomers are possible namely; Ortho, Meta and Para
compounds.
CH3
1
CH3 CH3
1 1
2 CH
3
4
3
CH3
CH3
1,2- Dimethylbenzene 1,3 - Dimethylbenzene 1,4-Dimethylbenzene
(o- Xylene) (m- Xylene) (p-xylene)
August Kekule in 1865 proposed the structure of benzene but Kekule structure of benzene fails to explains
unusual stability of benzene and preference to substitution reaction than addition reactions, which is
explained by resonance.
Resonance and stability of benzene: benzene is a hybrid of various resonating structures.
or
Aromaticity: Benzene is considered as parent of ‘aromatic compound’.The aromaticity of any compound is
decided by the following characteristics:
• Planarity
• Complete decolaclisation of the 𝜋 electrons in the ring.
• Presence of (4n + 2) 𝜋 electrons in the ring where n is an integer (n = 0, 1,2..) This is Huckel Rule.
Anthracene
Naphthalene
n = 2 ,10 pi ecelcetrons n=3 ,14 pi electrons
Preparation of Benzene : Benzene is commercially obtained from coal tar. In laboratory by the following
method:
1) Cyclic polymerisation of ethyne:
CH
CH
CH
Red hot iron tube
CH 873K
CH
CH Benzene
Ethyne
2)Decarboxylation of aromatic acids: Sodium salt of benzoic acid on heating with sodalime gives
benzene.
COONa
CaO +Na2CO3
+ NaOH
Heat
[Link] of Phenol: Phenol is reduced to benzene by passing its vapour over heated zinc dust.
OH
Heat
+ Zn + ZnO
Physical properties:
• Aromatic hydrocarbons are non – polar molecules.
• Usually colourless liquids or solids with characteristic aroma.
• Aromatic hydrocarbons are immiscible with water but readily miscible with organic solvents.
• They burn with sooty flame.
Chemical properties: Arenes are characterised by electrophilic substitution reaction, Under special
conditions they show addition and oxidation reaction.
Electrophilic substitution reaction:
(i) Nitration : When benzene is heated with the mixture of concentrated nitric acid and sulphuric acid
(nitrating mixture) nitrobenzene is formed.
NO2
323-333K
+ Conc.HNO3 + Conc.H2SO4 + H2O
Nitrobenzene
(ii) Halogenation: Arenes react with halogen in the presence of Lewis acid like anhydrous FeCl3,FeBr3 or
AlCl3 to yield haloarenes.
Cl
Anhyd.AlCl3
+ Cl2
+HCl
Chlorobenzene
(iii) Sulphonation: The replacement of hydrogen atom by a sulphonic acid group in a ring is called
sulphonation. It is carried out by heating benzene with fuming sulphuric acid (Oleum).
Fuming sulphuric acid is also known as oleum,Oleum is forms when sulphur trioxide is dissolved in
concentrated sulphuric acid.
SO3H
Heat
+ H2SO4(SO3) + H2O
Fuming sulphuric
acid
Benzene Sulphonic
acid
(iv) Friedel – Crafts alkylation reaction: When benzene is treated with alkyl halide in the presence of
anhydrous aluminium chloride, alkyl benzene is formed.
CH3
Anhyd.AlCl3
+ CH3Cl + HCl
Toulene
(v) Friedel – Crafts acylation reaction: The reaction of benzene with an acyl halide or acid anhydride in
the presence of lewis acids ( AlCl3) yields acyl benzene.
COCH3
Anhyd.AlCl3
+ CH3COCl + HCl
Acetylchloride Heat
Acetophenone
Cl
Cl Cl
Anhyd.AlCl3
+6Cl2 + 6HCl
Dark, Cold
Cl Cl
Cl
Hexachlorobenzene (Hexachlorobenzene = C6Cl6)
Electrophilic substitution mechanism( SE ) proceeds in three steps:
(i) Generation of the electrophile.
(ii) Formation of carbocation intermediate.
(iii)Removal of proton from the carbocation intermediate.
Mechanism of nitration of benzene:
1. Generation of electrophile:
H
+
HSO3O H + H O NO2 H O NO2 + HSO4
H
+
H O NO2 H2O
+ NO2
Nitronium ion
Protonated nitric ( Electrophile )
acid
2. Formation of carbocation: The electrophile nitronium ion attacks benzene ring to form
carbocation.( which is resonance stabilized).
+ NO2 NO2
Nitronium ion
Carbocation
3. Removal of proton: Loss of proton gives nitrobenzene .The proton is removed by HSO4–.
H
NO2
NO2 HSO4
+ H2SO4
Carbocation Nitrobenzene
Mechanism of chlorination of benzene: It occurs in three steps,
1. Generation of an electrophile:
Cl Cl + AlCl3 Cl + AlCl4
Chloronium
ion (Electrophile)
2. Formation of Carbocation: The electrophile chloronium ion attacks benzene ring to form
carbocation.(which is resonance stabilised).
H
Cl
+ Cl
Chloronium
ion (Electrophile)Carbocation
3. Removal of proton: Loss of proton gives chlorobenzene. The proton is removed by FeCl4–.
H Cl
AlCl4
Cl + AlCl3 + HCl
Chlorobenzene
Note: Similarly , explain the mechanism of friedel crafts alkylation, friedel crafts acylation, sulphonation of
benzene.
Addition reactions: Hydrogenation of benzene gives cyclohexane in the presence of nickel catalyst at high
temperature or pressure.
Ni
+ 3H2
Heat
Cyclohexane
Cl H
H Cl
uv Cl
+ 3Cl2 H
500K H Cl
Cl H
H Cl
Benzene hexachloride (BHC)
Gammaxane
Combustion: Benzene on heating in presence of air burns with sooty flame producing CO2 and H2O.
C6H6 + 15/2 O2 6CO2 + 3H2O
General equation :CXHY + ( x + y/4) O2 xCO2 + y/2 H2O
Directive influence of a functional group in monosubstituted benzene:
Depending on the nature of the substitutuent already present in the benzene two types of behaviour are
observed that is ortho and para products or meta products this is known as directive influence of
substituents.
Ortho and para directive groups: The groups which directs the incoming group to ortho and para positions
are called ortho and para directing [Link] eg: Phenolic (-OH ) group. Phenol is resonance hybrid of
following structures. They are known as activating [Link] examples are –NH2, -NHR,-NHCOCH3,-
OCH3,-CH3,-C2H5,-Cl etc.,
Meta directing group: The groups which direct the incoming group to meta position due to the electron
density on m- position is comparatively greater than –o and – p position in the benzene ring are called meta
directing groups. They are also knowns as deactivating groups. Other eg: -NO2,-CN,-CHO,-COR,-COOH,-
COOR,-SO3H etc.,
Carcinogenicity and Toxicity : The poly nuclear hydrocarbons are formed due to incomplete combustion
of organic materials like tobacco,coal and petroleum. They enter into human body and undergo various
biochemical reactions finally damage DNA and cause cancer ( Carcinogenic).
Examples for carcinogens: 1,2- Benzanthracene, 3- methylcholanthrene, etc.,
