CHAPTER – 30 (HYDROCARBONS)

BENZENE AND ITS COMPOUNDS

Reactions of Benzene / Reactivity of Benzene

 Unlike alkenes, benzene is resistant to addition reactions. This is because it involves breaking
the delocalized electron system and thus losing its stability.

 Instead, benzene undergoes substitution reactions. This involves replacing one or more
hydrogen atoms with another group of atoms.

 Benzene is particularly attractive to electrophiles due to its high electron density. Therefore
benzene mainly undergoes electrophilic substitution.

 The reactivity of benzene is also affected by the presence of other group(s) in the benzene
ring. This is known as substituent group effect, and it will be explained later.

Electrophilic substitution
 Electrophilic substitution is the replacement of an atom or a group of atom by an electrophile.
In benzene, the electrophile replaces the hydrogen atom(s).
 The general mechanism of electrophilic substitution:
Steps
1. Suppose, an electrophile X⁺ is generated from a compound XY. The electrophile is attracted
to the electron-rich region of the benzene ring.
2. Two electrons from the delocalised electron system are used to form a co-ordinate bond with
the electrophile.

3. An intermediate with the delocalised electron system partially broken is formed.

4. Y⁻ ion, from XY has a lone pair of electrons on it and it forms a bond with the hydrogen ion.
5. The hydrogen loses its electrons to the delocalised electron system to bond with Y⁻.
6. The delocalized electron system is now
restored.

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Reactions benzene
 Halogenation.
 Nitration.
 Alkylation (or acylation) of benzene (Friedel–Crafts reaction).
 Hydrogenation.

Halogenation
Reagent: Chlorine/bromine gas, Cl2/Br2
Condition: anhydrous (AlCl3 / AlBr3)

Mechanism

Nitration
Reagent: Concentrated nitric acid, HNO3
Condition: Reflux at a temperature 25 - 60 ºC and the presence of concentrated H2SO4 as
catalyst
Product: Nitrobenzene

50 - 55 ⁰C, con H2SO4

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Mechanism

Alkylation / Acylation (Friedel–Crafts reaction)

1. Alkylation
Reagent: Halogenoalkane
Condition: anhydrous AlCl3 + Heat
Product: Alkyl benzene

Mechanism

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 2. Acylation
Reagent: acyl Chloride
Condition: anhydrous AlCl3 + Heat
Product: acyl benzene

Hydrogenation
Reagent: Hydrogen gas, H2
Condition: Heat in the presence of nickel (Ni) / platinum (Pt) catalyst
Product: Cyclohexanes

*** In hydrogenation, hydrogen atoms are added to the benzene ring. The delocalised electron
system is permanently broken.

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 Substituent group effect on benzene ring
If a benzene already has a first substituent in it, second incoming substituent is affected by the nature
of the first substituent.
The first substituent has an effect on the position of the incoming second substituent.

 If X is an electron-withdrawing group, it deactivates the ring and it is 3-directing.

E.g. -NO2, -CN, -COOH, -CHO and -COR.
 If X is an electron-donating group, it activates the ring and it is 2,4-directing.
 E.g. -OH, -NH2, and alkyl (-CH3, -CH2) groups.

Reaction of alkyl benzene

Halogenation
Reagent: Cl2/Br2
Condition: AlCl3 or FeCl3 as catalyst

*** In the presence of UV light and the absence of halogen carriers (AlCl3 / FeCl3), the halogen is
substituted into the alkyl group via free-radical
substitution.

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Nitration
Reagent: Concentrated nitric acid
Condition: Reflux at a temperature 55 ºC and the presence of conc. H2SO4 as catalyst
Product: Nitro-alkylbenzene.

Oxidation
Reagent: Acidified potassium manganate(VII), KMnO4
Condition: Heat or reflux
Product: Benzoic acid

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Hydrogenation
Reagent: Hydrogen gas
Condition: Heat in the presence of nickel, Ni catalyst

Questions

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