On the mechanism of the reaction between aryl acetates and hydroxylamine

Abstract

The reaction of aryl acetates and hydroxylamine produces O-acylhydroxylamine and N-acylhydroxylamine, the latter being essentially observed for good leaving group esters and the former for poor leaving esters. For both acylation reactions, kinetics studies suggested a tetrahedral intermediate intervention for nucleofuges in a pKa range of 1 to 9. Esters having leaving groups with a pKa value less than 7 react by a rate-determining step inferred to be the tetrahedral intermediate formation, while for esters having leaving groups with a pKa value equal to or higher than 7, the rate-limiting step has been proposed to be the tetrahedral intermediate decomposition. General bifunctional acid-base catalysis by a second hydroxylamine molecule was identified as one of the components of the reaction for the intermediate collapse to products in the poor leaving group ester. ©ARKAT USA, Inc.