Intramolecular nucleophilic catalysis during alkaline hydrolysis of nonenolizable. beta.-keto esters

WN Washburn, ER Cook

Index: Washburn, William N.; Cook, Ewell R. Journal of the American Chemical Society, 1986 , vol. 108, # 19 p. 5962 - 5964

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Citation Number: 10

Abstract

Abstract: Kinetic and'* O-labeling studies demonstrate that in the hydrolysis of nonenolizable acetoacetate esters, the carbonyl hydrate acts as a nucleophilic catalyst. A cyclic four- membered lactone is formed and later opens. Structure/reactivity studies showed the rate- determining step to be a function of the pK, of the leaving group and the substituent bound to C, of the acetoacetate residue. Rate accelerations of 4 to IO4 were observed for ...