17953-83-2Relevant academic research and scientific papers
Intramoleclar Nucleophilic Catalysis during Alkaline Hydrolysis of Nonenolizable β-Keto-Esters
Washburn, William N.,Cook, Ewell R.
, p. 5962 - 5964 (2007/10/02)
Kinetic and 18O-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 pKa of the leaving group and the substituent bound to C3 of the acetoacetate residue.Rate accelerations of 4 to E4 were observed for hydrolyses of the corresponding p-nitrophenyl esters, depending on the substituent at C3.
