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The keto and enol forms are known as tautomers and they constantly interconvert (or tautomerize) between the two forms under acid or base catalyzed conditions. Both the reactions involve the same steps—protonation and deprotonation— although in the reverse order.

Figure1

The base-catalyzed reaction is initiated by the abstraction of the α hydrogen from the carbonyl compound. This abstraction forms a carbanion that is stabilized by delocalization of the negative charge across the carbonyl bond.

Figure2

The resonance results in a more stable enolate ion with negative change concentrated on the oxygen atom. The enolate ion thus formed is protonated to give the enol tautomer.

In acid-catalyzed keto–enol tautomerism, the acid protonates the carbonyl oxygen to form an oxonium ion intermediate. The oxonium ion undergoes resonance stabilization by moving the π electrons from the C=O bond towards the protonated oxygen. The α hydrogen is then deprotonated to form the enol tautomer.

Figure3

Tags
Keto enol TautomerismTautomersTautomerizationAcid catalyzed ReactionBase catalyzed ReactionProtonationDeprotonationCarbanionEnolate IonResonance StabilizationOxonium IonCarbonyl CompoundNegative ChargeEnol Tautomer

From Chapter 12:

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12.25 : Keto–Enol Tautomerism: Mechanism

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12.1 : Structures of Aldehydes and Ketones

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12.2 : IUPAC Nomenclature of Aldehydes

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12.4 : Common Names of Aldehydes and Ketones

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12.6 : NMR Spectroscopy and Mass Spectrometry of Aldehydes and Ketones

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12.7 : Preparation of Aldehydes and Ketones from Alcohols, Alkenes, and Alkynes

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12.8 : Preparation of Aldehydes and Ketones from Nitriles and Carboxylic Acids

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12.9 : Preparation of Aldehydes and Ketones from Carboxylic Acid Derivatives

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