The base-catalyzed tautomerization of acetylacetone in organic solvents. The correlation of the catalytic coefficient with the partition coefficient.

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The keto-enol tautomerization rate of acetylacetone catalyzed by triethylamine or tributylamine was observed in eight organic solvents, and the catalytic coefficient for each process of the ketonization and enolization was obtained. A remarkable solvent effect on the catalysis was discussed following the linear free-energy relationship between the catalytic coefficient and the liquid-liquid partition coefficients of the keto and enol forms. It was concluded that, in the homogeneous base-catalysis, the solvent affects the free-energy change of the transition state more greatly than those of the keto and enol forms. On the contrary, in the heterogeneous catalysis by the silica surface, the free-energy change of the keto and enol forms was suggested to be the main factor governing the kinetic solvent effect.
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