Aromatic Hydrocarbon
❑Aromatic Hydrocarbons
⮚ These hydrocarbons are also known as ‘arenes’ (Greek; aroma meaning pleasant
smelling). Most of such compounds were found to contain benzene ring.
⮚ Aromatic compounds containing benzene ring are known as benzenoids and those not
containing a benzene ring are known as non-benzenoids
⮚ Some examples of arenes are given below.
❑ Characteristics of aromatic compound:
1. Cyclic organic compounds having planer ring.
2. Highly unsaturated
3. Undergo electrophilic substitution reaction but resistant to addition
reaction.
4. Less reactive than aliphatic compounds.
5. Percentage of carbon is high . Hence burn with sooty flame.
6. Follow Huckels rule (4n+2 π ).
Huckel's Rule:
⮚ Pi electrons are defined as electrons that participate in pi bonds or lone
pairs within p orbitals.
⮚ The pi-electron count is defined by the series of numbers generated from
4n+2 where n = zero or any positive integer (i.e., n = 0, 1, 2, etc.). This
rule is known as Huckel’s rule.
4n+2 = nπ
Crieteria for aromaticity
• When deciding if a compound is aromatic, go through the following checklist. If the
compound does not meet all the following criteria, it is likely not aromatic.
• The molecule is cyclic (a ring of atoms)
• The molecule is planar (all atoms in the molecule lie in the same plane)
• The molecule is fully conjugated (p orbitals at every atom in the ring)
• The molecule has 4n+2 π electrons (n=0 or any positive integer)
Some Examples
Structure of Benzene (given by Kekule):
⮚ By elemental analysis, it is found that molecular formula of benzene is C 6H6. This
indicates that benzene is a highly unsaturated compound. In 1865, Kekule gave the cyclic
planar structure of benzene with six carbons with alternate double and single bonds.
⮚ Kekule Structure for benzene is quite satisfactory in explaining of many known
reactions, e.g.
The Kekule structure indicates the possibility of two isomeric 1,2-dibromobenzenes. In
one of the isomers, the bromine atoms are attached to the doubly bonded carbon atoms
whereas in the other they are attached to the singly bonded carbon.
In fact, only one ortho-dibromobenzene could be prepared.
To overcome this problem Kekule suggested that benzene was a mixture of two forms.
Failure of Kekule’s structure: Kekule structure of benzene failed to explain the unique
stability and its preference to substitution reaction than addition reactions.
Q. Write down the drawbacks of Kekule’s Structure of benzene??
Resonance Structure of Benzene:
⮚ The phenomenon in which two or more structures can be written for a substance which involve
identical positions of atoms is called resonance.
⮚ In benzene’s Kekule’s structures (1) and (2) represent the resonance structures. Actual structure – of the
molecule is represented by hybrid of the these two structures.
Orbital structure of benzene:
⮚ All six carbon atoms in benzene are sp2 hybridized. The sp2 hybrid orbitals overlap with each other and
with s orbitals of the six hydrogen atoms forming C—C and C—H σ-bonds.
⮚ The data indicates that all the six C—C bond length are of
the same order (139 pm) which is intermediate between (C—
C) single bond (154 pm) and C—C double bond (133 pm).
Thus the presence of pure double bond in benzene gives the
idea of reductance of benzene to show addition reaction under
normal condition. The is, It explains the unusual behaviour of Showing overlap of p orbitals
benzene.
❑Nomenclature and Isomerism
⮚ All six hydrogen atoms in benzene are equivalent; so it forms one and only one type of
monosubstituted product. When two hydrogen atoms in benzene are replaced by two
similar or different monovalent atoms or groups, three different position isomers are
possible.
⮚ The 1, 2 or 1, 6 is known as the ortho (o–), the 1, 3 or 1, 5 as meta (m–) and the 1, 4 as
para (p–) disubstituted compounds.
# A few examples of derivatives of benzene are;
1.
2.
❑Preparation of Benzene:
⮚ Benzene is commercially isolated from coal tar. However, there are some
synthetic methods which is applied in the laboratory for the preparation of
benzene.
❑Physical Properties of Benzene:
(i) Benzene is a colourless liquid.
(ii) It is insoluble in water. It is soluble in alcohol, ether, chloroform etc.
(iii) Benzene itself is a good solvent for many organic and inorganic
substances e.g., fat, resins, sulphur and iodine.
(iv) It bums with a luminous, sooty flame in contrast to alkanes and
alkenes which usually bum with a bluish flame.
(v) Boiling point 80.4 0 C and melting point 5.5 0 C.
Chemical Properties of Benzene
⮚ Arenes are characterised by electrophilic substitution reactions. However, under
special conditions they can also undergo addition and oxidation reactions.
Electrophillic Substitution Reactions:
Benzene undergoes typical electrophillic substitution reactions due to the retention
of resonance stabilization of the ring (aromaticity). Some common electrophillic
substitution reactions of benzene are:
– Halogenation,
– Nitration,
– Friedal Craft’s alkylation
– Friedal Craft’s acylation Reactions
– Sulphonation
Halogenation reaction:
⮚ The replacement of a hydrogen atom by a halogen atom such as fluorine, chlorine,
bromine and iodine in the presence of a Lewis acid such as anhydrous aluminium
chloride or ferric chloride or ferric bromide is called halogenation of benzene.
⮚ Chlorination and bromination which occur at a temperature between 310 and
320 K Benzene is treated with chlorine in the presence of anhydrous aluminium
chloride results in the formation of chloro benzene.
Iodination
Iodination carried out in the
presence of conc. HNO3 and HIO3
+ H2 O
❑Nitration:
⮚ Reactions, in which hydrogen atom in the benzene ring is replaced by
the nitro group is known as nitration.
⮚ Nitration is carried out by heating benzene at about 330 K with the
nitrating mixture consisting of concentrated HNO₃ and concentrated
H₂SO₄.
+ H2 O
❑Sulphonation
⮚ When the hydrogen atom in a Benzene ring is replaced by the
sulphonic acid (-SO₃H) group, is known as Sulphonation.
⮚ Sulphonation reaction is carried out by heating Benzene with fuming
sulphuric acid or oleum. Sulphonation can also be carried out by
treating benzene with chloro sulphonic acid.
❑Friedal-Crafts alkylation reaction:
⮚ Reactions in which the hydrogen atom in Benzene ring is replaced by
the alkyl group in the presence of anhydrous aluminium chloride
known as Friedal-crafts alkylation reaction.
❑Friedal-Crafts acylation:
⮚ When benzene is treated with acyl halide or acid anhydride in the
presence of anhydrous aluminium chloride, hydrogen atom in a
benzene ring is replaced by the acyl group and forms acyl benzene.
This reaction is called the Friedal-Crafts acylation.
methyl phenyl ketone
Review:
(v) Friedal-Crafts acylation:
❑ Addition reaction
stabilization due to presence of delcalization of π electron.
⮚ Benzene is less reactive towards addition reaction because of
⮚ In the presence of light, heat, pressure, catalyst
aromaticity of benzene is lost.
1. Catalytic hydrogenation(reduction):
Benzene reacts with hydrogen in the presence of heated nickel as
catalyst to give cyclohexane.
2.Addition of halogen
Benzene reacts with Cl2 and Br2 in the presence of sunlight to give
benzene hexachloride and benzene hexabromide.
i)
BHC (Benzene hexachloride) is used as insecticide.
ii) with Br2 ?????
3. Addition of ozone followed by hydrolysis:
Benzene reacts with ozone to form benzene triozonide which on
hydrolysis in the presence of Zn dust gives glyoxal.
❑ Oxidation reactions:
1. Combustion
⮚ Benzene is completely oxidized to carbon dioxide and water when it
2C6 H6 + 15 O2 → 12CO2 + 6H2 O
burns in free supply of air. It burns with sooty flame.
2. Catalytic oxidation
⮚ Partial oxidation of benzene in the presence of V2 O5
gives maleic anhydride.
+ 4CO2 + 4H2 O
Orientation in Benzene derivatives:
Activating groups or Ortho para director: These group activates the benzene ring for the
attack by an electrophile. The groups which direct the incoming group to ortho and para
position are called ortho para directing groups.
Example, —OH; —NH2, —NHR, —NHCOCH3, —OCH3 —CH3 —C2H5 etc.
Deactivating groups or Meta directing group: :
Due to deactivating group because of strong —I effect, overall electron density on
benzene ring decreases. It makes further substitution difficult.
The groups which direct the incoming group to meta position are called meta directing
groups.
Example: N02, —CN, —CHO, —COR, —COOH, —COOR, -S03H etc.
(Deactivating groups)
Practice
1. 3.
2.
4.
Uses of Benzene:
As a Solvent
• Benzene is commonly used as a solvent in many industrial, commercial and research. Manufacturers use
products which contain benzene as solvents in various production stages and it is used in manufacturing
chemical and plastic products. Few examples include resins, synthetic products such as nylon, Styrofoam
and others. Benzene is also used in the production of asphalt that is used by roofing and paving companies.
Benzene as an Intermediate
• Benzene is also used in the production of tires and rubber and it is found in adhesives that are used to glue
soles to shoes. Further chemical compounds that are manufactured using Benzene include detergents,
pesticides insecticides, herbicides, and dyes.
Printing Industry
• If you didn’t know, Benzene is found in most products that is used in the printing industry. There are
products that contain this chemical and are further used specially for cleaning printing equipments which
also makes them last longer and functional. Additionally, ink and variety of painting products, such as
spray paints, sealers, lacquers and stains also contain some portion of benzene. It keeps the paints in liquid
form.
As a Fuel
• Due to the high octane number and natural availability, Benzene is used as a fuel by a lot of people and
manufacturers. Some have used it as a gasoline additive to help burn fuel more efficiently.
Practice Question
