ESR spin-trap study of the radicals present during the thermolysis of some novel alkyl peroxy esters.

Abstract

The thermolysis of four alkylperoxy esters was undertaken at various temperatures between 300 and 353 K and the radicals generated were trapped employing DMPO, DEPMPO, PBN-d14 and TTBNB. The adducts of a range of second-generation carbon-centred radicals, formed via decarboxylation of the acyloxyl moiety, including those of the 2,4,4-trimethylpentyl and hept-3-yl radicals, were also observed. The co-generated tert-alkoxyl radicals, released during the thermolysis of tert-butylperoxy-3,3,5-trimethylhexanoate, tert-amylperoxy-2-ethylhexanoate and the bifunctional peroxide 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, were all successfully trapped, as were a range of second-generation carbon-centred radicals formed following -scission of these tert-alkoxyl radicals