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ESR spin‐trap study of the radicals present during the thermolysis of some novel alkyl peroxy esters
Author(s) -
Mekarbane Pierre G.,
Tabner Brian J.
Publication year - 2000
Publication title -
magnetic resonance in chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.483
H-Index - 72
eISSN - 1097-458X
pISSN - 0749-1581
DOI - 10.1002/1097-458x(200010)38:10<845::aid-mrc746>3.0.co;2-v
Subject(s) - chemistry , radical , peroxide , alkoxy group , photochemistry , thermal decomposition , decarboxylation , moiety , adduct , alkyl , bifunctional , medicinal chemistry , decomposition , organic chemistry , catalysis
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 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 β‐scission of these tert ‐alkoxyl radicals. Copyright © 2000 John Wiley & Sons, Ltd.