Peroxide Effect In Addition Reactions
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.
Select the correct option:
Solution
Anti-Markovnikov addition giving 1-bromobutane via a free radical mechanism
The peroxide or Kharasch effect reverses the normal orientation of HBr addition to alkenes, and it operates only with HBr, not with HCl or HI. Peroxides initiate a free radical chain: they decompose to give radicals that abstract hydrogen from HBr, generating bromine radicals. The bromine radical adds to the terminal carbon of but-1-ene because that produces the more stable secondary carbon radical CH3−CH2−CH∙−CH2Br rather than a primary one. This radical then abstracts hydrogen from another HBr 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 HBr addition. The reason the effect is limited to HBr is energetic: for HCl the hydrogen-abstraction step is endothermic and for HI the halogen-addition step is endothermic, so neither sustains an efficient chain, whereas both propagation steps for HBr are exothermic. This follows the NCERT account of the peroxide effect and connects radical stability with reaction orientation. A consistency check: only HBr shows this effect because its bond energetics make both radical steps exothermic.
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About This Question
- Subject
- chemistry
- Chapter
- hydrocarbons
- Topic
- peroxide effect in addition reactions
- Difficulty
- Medium
- Year
- 2025
Solution
Correct Answer:
Anti-Markovnikov addition giving 1-bromobutane via a free radical mechanism
The peroxide or Kharasch effect reverses the normal orientation of HBr addition to alkenes, and it operates only with HBr, not with HCl or HI. Peroxides initiate a free radical chain: they decompose to give radicals that abstract hydrogen from HBr, generating bromine radicals. The bromine radical adds to the terminal carbon of but-1-ene because that produces the more stable secondary carbon radical CH3−CH2−CH∙−CH2Br rather than a primary one. This radical then abstracts hydrogen from another HBr 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 HBr addition. The reason the effect is limited to HBr is energetic: for HCl the hydrogen-abstraction step is endothermic and for HI the halogen-addition step is endothermic, so neither sustains an efficient chain, whereas both propagation steps for HBr are exothermic. This follows the NCERT account of the peroxide effect and connects radical stability with reaction orientation. A consistency check: only HBr 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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