13.16 : CO2로 카르복시 그룹의 손실: β-케토산의 탈카르복실화

Carboxylic acids bearing a keto group at the β position to the carboxyl group are called β-keto acids. When heated, these acids can readily undergo decarboxylation to lose CO₂ gas while simultaneously generating a ketone.

The decarboxylation mechanism begins with the intramolecular hydrogen bonding between the β-keto oxygen atom and the hydrogen atom of the carboxyl group, which generates a reactive conformation.

As the partially protonated keto-oxygen is highly electrophilic, it leads to an internal electron transfer, proceeding through a six-membered cyclic transition state.

Consequently, a C–C bond cleavage results in the formation of an enol, along with the evolution of CO₂ as gas.

Finally, the enol undergoes facile keto-enol tautomerism to yield more stable ketones.