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Arrange the following in increasing order of their reactivity for nucleophilic addition reaction

ChemistryHydrocarbonsAP EAMCETAP EAMCET 2022 (04 Jul Shift 1)
Options:
  • A a<b<c<d
  • B a<d<c<b
  • C c<b<a<d
  • D c<a<b<d
Solution:
1816 Upvotes Verified Answer
The correct answer is: a<b<c<d

Aldehydes are generally more reactive than ketones in nucleophilic addition reactions due to steric and electronic reasons. Sterically, the presence of two relatively large substituents in ketones hinders the approach of nucleophile to carbonyl carbon than in aldehydes having only one such substituent. Electronically, aldehydes are more reactive than ketones because two alkyl groups reduce the electrophilicity of the carbonyl carbon more effectively than in former.

Benzophenone being a ketone is the least reactive towards nucleophilic addition. All others are aldehydes. Among them, p-tolualdehyde is less reactive than benzaldehyde because CH3 group present at the para position w.r.t.  -CHO group will increase the electron density on the carbonyl carbon atom due to hyper conjugation effect. As a result, the nucleophile attack occurs to lesser extent as compared to benzaldehyde.

In p-nitrobenzaldehyde, the nitro group has an opposing effect. It is electron withdrawing in nature due to -I effect as well as -R effect. The electron density on the carbonyl carbon atom decreases and this favours the nucleophile attack.

Hence, the correct order of reactivity towards nucleophilic substitution reaction is Benzophenone < p-tolualdehyde < benzaldehyde < p-nitrobenzaldehyde

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