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Peroxide Effect In Addition Reactions

Mediumchemistry

Addition of hydrogen bromide to but-1-ene proceeds in the presence of benzoyl peroxide, and the observed orientation of the product must be explained mechanistically.

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About This Question

Subject
chemistry
Chapter
hydrocarbons
Topic
peroxide effect in addition reactions
Difficulty
Medium
Year
2025
Tags
peroxide effectKharasch effectanti-Markovnikovfree radical additionradical stability

Solution

Correct Answer:

Anti-Markovnikov addition giving 1-bromobutane via a free radical mechanism

The peroxide or Kharasch effect reverses the normal orientation of addition to alkenes, and it operates only with , not with or . Peroxides initiate a free radical chain: they decompose to give radicals that abstract hydrogen from , generating bromine radicals. The bromine radical adds to the terminal carbon of but-1-ene because that produces the more stable secondary carbon radical rather than a primary one. This radical then abstracts hydrogen from another molecule, placing hydrogen on the internal carbon and giving 1-bromobutane, the anti-Markovnikov product. The Markovnikov option is wrong because peroxides switch the mechanism from ionic to radical, changing the regiochemistry. The third option pairs the correct product with the wrong mechanism, since anti-Markovnikov orientation here arises from radicals, not carbocations. The claim of no reaction is false because peroxides actually accelerate addition. The reason the effect is limited to is energetic: for the hydrogen-abstraction step is endothermic and for the halogen-addition step is endothermic, so neither sustains an efficient chain, whereas both propagation steps for are exothermic. This follows the NCERT account of the peroxide effect and connects radical stability with reaction orientation. A consistency check: only shows this effect because its bond energetics make both radical steps exothermic.

This medium difficulty chemistry question is from the chapter hydrocarbons, covering the topic of peroxide effect in addition reactions. It appeared in the 2025 exam.

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