Hydrolysis of Esters and Amides in Strongly Basic Solution. Evidence for the Intermediacy of Carbanions

Article abstract of DOI:10.1021/jo00319a028

Kinetic studies of the decomposition of the carbaninons derived from a number of esters and amides of p-nitrophenylacetic acid in strongly basic solution have been carried out.Kinetic solvents isotop effects and the large Hammett ρ value for substituents on the aromatic ring of substituted phenyl esters of p-nitrophenylacetic acid suggest decomposition occurs by an E1cB mechanism.Furthermore, it appears that the carbanion can decompose by either an ionic or a free-radical mechanism, depeneding on the nucleofugality of the leaving group.An intermediate predicted to be 4-nitrophenyl ketone ha been detected spestroscopically in a number of cases.