A convenient preparation of aqueous methyl hydroperoxide and a comparison of its reactivity towards triacetylethylenediamine with that of other nucleophiles: the mechanism of peroxide bleach activation

Abstract

A less hazardous preparation of aqueous methyl hydroperoxide is described. The nucleophilic second-order rate constants for the reactions of triacetylethylenediamine (triAED) with a limited range of alkoxides, amines and peroxides exhibit Brønsted β-values of 0.7, 0.8 and 1.0 respectively. These values are consistent with transition states in which cleavage of one of the imide bonds of triAED is important. The rate constant for hydrogen peroxide shows a positive deviation from the Brønsted plot for the other peroxides. It is suggested that the hydrogen atom of the hydroperoxide anion causes the rate enhancement by hydrogen-bonding to the nitrogen of triAED. The results give an important insight into the mechanism of peroxide bleach activation.