Control of the ‘extended’E1cB mechanism of acyl group transfer in activated esters of acrylic acids

Abstract
Aminolysis and alkaline hydrolysis of aryl propenoates are shown to proceed via a normal nucleophilic substitution mechanism. The ‘extended’E1cB mechanism of hydrolysis involving attack of hydroxide ion at the β carbon followed by expulsion of the phenolate ion from the resulting carbanion is shown not to occur with the parent propenoate. The ‘extended’E1cB mechanism is taken by the hydrolysis of 2-cyano-3-(4-methoxyphenyl)propenoate esters due to the stabilising effect of the cyano-group on the intermediate carbanion.

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