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

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-d(14) 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 teut-alkoxyl radicals, released during the thermolysis of terr-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 beta-scission of these tert-alkoxyl radicals. Copyright (C) 2000 John Wiley & Sons, Ltd.