Arenes and Aromaticity: Example: Alkyl Benzenes

ARENES AND AROMATICITY
Arene is generally used for aromatic hydrocarbons. Benzene and its alkyl derivatives are important
parts of arenes. The general formula of arenes is CnH2n-6y (where y =Number of rings) so the percentage
of carbon in arenes is more than that of aliphatic hydrocarbons. Aromatic compounds are now regarded
as a class of compound which contains at least one benzene ring. They are also known as benzenoids. In
other cases compound which do not contain benzene ring but they still behave as aromatic compounds.
Such compounds are known as non-benzenoids. In this series benzene is first and most important
member. These are called benzenoid compounds.
Example:
Alkyl benzenes:
•Alkenyl benzenes:
Aromatic hydrocarbons which have different chemical properties than benzene are
called non benzenoid aromatic compound.
Example:
NOMENCLATURE OF BENZENE DERIVATIVE
1. Monosubstituted benzene: These are named by prefixing the name of the substituent to ‘benzene’.
Example:
2. Disubstituted benzene: When there are two substitutents on the ring, three positional isomers
are possible and their positions are indicated by ortho, meta and para or by numbers.
Example:
3. Polysubstituted benzene: When three or more substituent are placed on benzene then numbers
are used to indicate the position.
Example:
4. Fused polycyclic arenes: There are many polycyclic arenes having one or more benzene
rings fused in ortho positions.
Example:
THE ARYL GROUP
The univalent group which is derived by any other aromatic hydrocarbon is known as aryl group (Ar-).
Example:
AROMATIC NUCLEUS AND SIDE CHAIN

The basic carbon structure of benzene is called aromatic nucleus. When alkyl group attached
to the aromatic ring is called side chain.
STRUCTURE OF BENZENE
Kekule structure of benzene:

In 1865, a scientist Kekule gives the special structure of C6H6 and he represents that C6H6 shows
two resonating structures which are known as Kekule structures and these structures cannot explain
all properties of benzene so they have resonance hybrid and the resonating energy for it is 36
kcal/mol.
It is cyclic planar structure of six carbons with alternate single and double bonds. Each carbon
attached with one hydrogen so two structures are in a state of continuous oscillation.
RESONANCE AND MO PICTURE
•Resonance Structure:
According to valence bond theory, benzene is considerd as resonance hybrid of two

kekule and three dewar structures, the kekule structure making major contributions.
Because resonating structures are more stable so benzene should be more stable than
other structure.
•Molecular Orbital (MO) picture:
All six carbon atoms in benzene are sp2 hybridized. All hybrid orbitals overlap each other and with
s-orbitals C-C and C-H bonds to form σ bond. It is the modern view of structure, in benzene each
carbon is sp2 hydrides with bond angle 120˚. So it is cyclic and planar. Each carbon contains one
unhybrid p orbital (pz) which is perpendicular to the σ plane and π-e- undergoes delocalization,
each carbon is overlap with two carbon atoms to form sp2-sp2 σ bond and with H-atom to form sp2-s
σ bond.
π-Frame work of benzene:
Complete structure of benzene:

AROMATICITY: THE HUCKEL’S RULE
Aromaticity is characterized by stability, whereas antiaromaticity is characterized by instability.

Aromatic compound > cyclic compound with localized electrons > antiaromatic compound
The aromatic compounds have alternate single and double bond due to this those compounds
have special stability, which is known as Aromaticity. These are the following rules for
compound to be aromatic.
1. An aromatic compound is cyclic and planar.

2. There is a p-orbital on every atom of an aromatic ring.
3. The cyclic arrangement of p-orbitals in an aromatic compound, must contain (4n+2) π
electrons. This is known as Huckel rule. If such systems contain 4nπ electron then it will be anti-
aromatic.
Example:
METHODS OF PREPARATION
1. From sodium benzoate:

From sodium benzoate C6H5COONa on react with sodalime (NaOH and CaO) to give benzene.
2. From Phenol:
Phenol on react with Zn power gives benzene by removing ZnO.
3. From Grignard Reagent: Grignard Reagent (C6H5X) on hydrolysis gives benzene.

4. From Benzene sulphonic acid: Benzene sulphonic acid on hydrolysis gives benzene.
5. From acetylene (By polymerization reaction): Acetylene (Ethyne) on polymerization

gives benzene.
6. Industrial Preparation of benzene: n-hexane on heating at 500˚C temperature in the

presence of Cr2O3 supplied by Al2O3 gives cyclohexane, which on again dehydrogenation
gives C6H6.
PROPERTIES (PHYSICAL AND CHEMICAL)
A. Physical properties:
1. Benzene is a colorless liquid

2. It is insoluble in liquid but soluble in Organic solvent.
3. Benzene itself is a good solvent.
4. Its vapour is poisonous.
B. Chemical properties of benzene:
1. Hydrogenation: In the presence of Ni catalyst at 160˚C temperature benzene on react with H2

gives an additional product cyclohexane.
2. Ozonolysis: In the presence of CCl4 benzene on react with O3 gives benzene tri-ozonoid.
This on hydrolysis in the presence of Zn gives glyoxal.
3. Chlorination: In the presence of sun light, benzene on reaction with Cl2 gives an additional
product benzene hexa chloride (C6H6Cl6, BHC). It is also known as Gamaxine, lindane or 666. It is
used as apestiside
4. Electrophilic Substitution reaction:
i. Chlorination: In the absence of sun light and in the presence of FeCl3 or AlCl3, benzene on react
with Cl2 gives C6H5Cl. This reaction known as electrophilic substitution reaction of benzene.
Mechanism:
Step I: Formation of electrophile: Step III: Formation of product:
Step II: Attack of electrophile (formation of Step IV: Formation of catalyst:

arinium ion):
ii. Nitration: In the presence of H2SO4 benzene on react with HNO3 gives nitrobenzene. This
reaction is known as nitration.
Mechanism:
Step II: Attack of Electrophile (NO2+) Step IV: Formation of catalyst:

iii. Sulphonation: In the presence of H2SO4, benzene on react with H2SO4 gives benzene
sulphonic acid. This reaction is known as sulphonation reaction.
Mechanism:
Step II: Attack of electrophile: Step IV: Formation of catalyst:

iv. Friedel Craft reaction:
a. Friedel craft alkylation: In the presence of anhydrous AlCl3, benzene reacts with R-X to
give alkyl benzene. This reaction is known as Friedel Craft acylation.
Mechanism:

b. Friedel craft acylation: In the presence of anhydrous AlCl3, benzene reacts with R-CO-X
to give acetophenone. This reaction is known as Friedel Craft acylation.
Mechanism:

Reduction of benzene (Birch reduction)
The Birch reduction is an organic reaction where aromatic rings undergo a 1,4-reduction to provide
unconjugated cyclohexadienes. The reduction is conducted by sodium or lithium metal in liquid
ammonia and in the presence of an alcohol.
Mechanism:
Orientation and ortho/para ratio
As we know that all six hydrogen atoms are identical. So they form only monosubstituted derivative.
The next incoming electrophile will forward to the other position by the I substituent group. Hence,
“The tendency of I substituent group for farwarding the II incoming substituent group on ortho, para
or meta positions is known as directive influence.” Directive influence depends upon the nature of I
substituent group. Classification of groups according to directive influence: According to directive
influence the groups are classify into two classes-
(1) Ortho para director.

(2) Meta director.
In a C6H6 ring the position 2, 6 are equivalent and form ortho product. The position 3, 5 are equivalent
and gives meta product. The position 4 is unique and gives para product.
Ortho/para directing: If the first substituent group forward to the incoming second substituent group
primarily to ortho and para position then it is known as o, p director.
Example: When C6H5OH undergoes nitration then it form 57% o-nitro phenol and 43% p-nitro
phenol.
Condition for o-p director:
1. o, p-directors are saturated in nature.
2. They are electron rich, hence they consist lone pair of electrons (except –R groups).
3. These are ring activator (except, halogen family due to –I effect.
Examples of o,p-directors-
Strongly activator- Weak activator- Ring deactivator-

-OH, -NH2, -R2N ,-OR -CH3, -C2H5, -R -F, -Cl, -Br, -I
Mechanism of o, p-director: The mechanism of o, p-director group increases the density of e- at o, and
p-position due to which the incoming electrophile will easily attack at those positions. Hence these are
ring activator.
Meta-directors- If the first substituent groups forward to the incoming substituent group at
meta position then it is referred as meta director.
Example: When undergoes nitration then it form 1, 3 dinitro benzene.
Condition for meta directors-

(1) They are multi bonded (except –NR3+).
(2) These are electron deficient.
(3) These are ring deactivators because they withdraw the electron from the ring towards itself.
Examples of Meta directors:

-NO2, - COOH, - CHO, -SO3H, CONH2, -CN, -NR3+ etc.
Mechanism of meta directors:
Thus is is clear from above mechanism that m-directors withdraw the electron from ring. As a
result the ortho and para position becomes partially + ve. Hence the incoming second
electrophile will attack at neutral meta position. So these are meta directors and also ring
deactivator.

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ARENES AND AROMATICITY

AROMATIC NUCLEUS AND SIDE CHAIN

Kekule structure of benzene:

According to valence bond theory, benzene is considerd as resonance hybrid of two

Complete structure of benzene:

Aromaticity is characterized by stability, whereas antiaromaticity is characterized by instability.

1. An aromatic compound is cyclic and planar.

1. From sodium benzoate:

3. From Grignard Reagent: Grignard Reagent (C6H5X) on hydrolysis gives benzene.

5. From acetylene (By polymerization reaction): Acetylene (Ethyne) on polymerization

6. Industrial Preparation of benzene: n-hexane on heating at 500˚C temperature in the

1. Benzene is a colorless liquid

B. Chemical properties of benzene:

1. Hydrogenation: In the presence of Ni catalyst at 160˚C temperature benzene on react with H2

Step I: Formation of electrophile: Step III: Formation of product:

Step II: Attack of electrophile (formation of Step IV: Formation of catalyst:

Step I: Formation of electrophile: Step III: Formation of product:

Step II: Attack of Electrophile (NO2+) Step IV: Formation of catalyst:

Step I: Formation of electrophile: Step III: Formation of product:

Step II: Attack of electrophile: Step IV: Formation of catalyst:

Step I: Formation of electrophile: Step III: Formation of product:

Step II: Attack of electrophile: Step IV: Formation of catalyst:

Step I: Formation of electrophile: Step III: Formation of product:

Step II: Attack of electrophile: Step IV: Formation of catalyst:

(1) Ortho para director.

Strongly activator- Weak activator- Ring deactivator-

Example: When undergoes nitration then it form 1, 3 dinitro benzene.

Condition for meta directors-

Examples of Meta directors:

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