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Tautomerism

Mediumchemistry

In keto-enol tautomerism, the interconversion between the two forms specifically involves the migration of which atom along with a shift of bonding?

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About This Question

Subject
chemistry
Chapter
some basic principles of organic chemistry
Topic
tautomerism
Difficulty
Medium
Year
2025
Tags
tautomerismketo enol equilibriumproton migrationalpha hydrogenconstitutional isomers

Solution

Correct Answer:

A hydrogen atom from carbon to oxygen

Tautomerism is a special type of isomerism in which two constitutional isomers interconvert rapidly by the relocation of a proton accompanied by the reorganisation of pi bonds. In keto-enol tautomerism the keto form has a carbonyl group and an alpha C-H bond, while the enol form has a C=C double bond and an O-H group. The conversion proceeds by transfer of the alpha hydrogen from carbon to the carbonyl oxygen, together with movement of the double bond from C=O to C=C. The option describing migration of a hydroxyl group is wrong because tautomerism moves a hydrogen, not an intact -OH. The shift of a methyl group between carbons would be a skeletal change, not tautomerism, so that is incorrect. Movement of a full carbonyl carbon would break the molecular skeleton and is not what occurs. This proton-shift mechanism is exactly how NCERT describes keto-enol equilibrium, in which the keto form usually predominates because the carbonyl C=O bond is stronger than the enol C=C bond. The enol content rises sharply in systems such as 1,3-dicarbonyl compounds, where the enol is stabilised by conjugation and intramolecular hydrogen bonding. Tautomers are genuine isomers, not resonance structures, because atoms actually move. Plausibility check: only a small, mobile hydrogen can migrate fast enough to give the dynamic equilibrium characteristic of tautomers, confirming the hydrogen transfer.

This medium difficulty chemistry question is from the chapter some basic principles of organic chemistry, covering the topic of tautomerism. It appeared in the 2025 exam.

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