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Question -

Addition of HBr to propene yields 2-bromopropane, while in presence of benzoyl peroxide, the same reaction yields 1-bromopropane. Explain and give mechanism.



Answer -

Additionof HBr to propene is an ionic electrophilic addition reaction in which theelectrophile, i.e., H+ first adds to give a more stable 2°carbocation. In the 2nd step, the carbocation is rapidly attacked by thenucleophile Br~ ion to give 2-bromopropane.

In presence of benzoyl peroxide, the reaction is still electrophilic but theelectrophile here is a Br free radical which is obtained by the action ofbenzoyl peroxide on HBr

In the first step, Br radical adds to propene in such a way so as to generatethe more stable 2° free radical. In the second step, the free radical thusobtained rapidly abstracts a hydrogen atom from HBr to give 1-bromopropane.

From the above discussion, it is evident that although both reactions areelectrophilic addition reactions but it is due to different order of additionof H and Br atoms which gives different products.

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