Anti-Markonikov rule Kharasch effect the basis of appropriate mechanism.

on
17. Explain the
or

Kharasch eflect is the addition ofonly HBr to alkenes in the presence of benzoyl peroxide to give
Ans.
the product agaimst the Markownikov rule. For example,
CH,CH = CH, + HBr Benzoyl peroxide - CH,-CH-CH,-Br

P'ropene I-Bronopropane

The addition of HBr to unsymmetrical alkene in the presence of benzoyl peroxide occurs by free
radical mechanism. The various steps of this mechanism are
) Benzoyl peroxide undergoes homolytic fission to produce CgH,-CO-0' free radical.
CHCO-0-0-COC, Homolysis - CH,cO-O +0-COC,H,
Benzoyl peroxide Free radical Free radical

i) Free radical CgH,CO-O reacts with HBr to generate free radical Br.

CHCO-0 + H-Br C,H,COOH + Br

Free radical
Free radical Benzoic acid

(ii) Then the free radical Br adds to double bond in such a way to give more stable free radical.
Since 2° free radical is more stable than 1° free radical, it is preferably formed.

Br +CH-CH =
CH, »
CH-CH-CH,Br + CH-CH-CH2
Propenee 2°Free radical
(more stable) Br
1° free radical
(less stable)

(v) The 2° free radical abstracts a Br free radical from HBr resulting in the formation of
anti-Markownikov product.

CH,CH-CH,Br + HBr -CH,CH,-CH,Br +Br

2 free radical 1-Bromopropane
The steps (iü) and (iv) are repeated again and again to form the desired product.