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ESR spin-trap study of the radicals present during the thermolysis of some bis(tert-alkylperoxy)alkanes and bis(tert-alkylperoxy)cycloalkanes.

Mekarbane, Pierre G. and Tabner, Brian J. (2000) ESR spin-trap study of the radicals present during the thermolysis of some bis(tert-alkylperoxy)alkanes and bis(tert-alkylperoxy)cycloalkanes. Magnetic Resonance in Chemistry, 38 (3). pp. 183-191. ISSN 0749-1581

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Abstract

The thermolysis of three bis(tert-alkylperoxy)alkanes and two 1,1-bis(tert-alkylperoxy)cycloalkanes was undertaken at various temperatures between 333 and 383 K and the radicals generated trapped employing DMPO, DEPMPO, PBN-d14 and TTBNB. The appropriate tert-alkoxyl radical was trapped during the thermolysis of all five peroxides and underwent -scission to give the appropriate alkyl radical and ketone. Although the appropriate sister O-centred 1-(tert-alkylperoxy)alkoxyl radicals (3) were not trapped, adducts of the radicals derived from them via -scission were observed. The ethyl radical was trapped during the thermolysis of 2,2-bis(tert-butylperoxy)butane (1a) and the ethoxycarbonylmethyl radical during the thermolysis of both ethyl-3,3-bis(tert-butylperoxy)butyrate (1b) and ethyl 3,3-bis(tert-amylperoxy)butyrate (1c), thus establishing the thermolysis scheme for these bis(tert-alkylperoxy)alkanes. In the case of 1,1-bis(tert-butylperoxy)cyclohexane (2a) it has been established that the sister O-centred [1-(tert-butylperoxy)cyclohexyl]oxyl radical (6a) undergoes a rapid ring-opening reaction to give the 5-(tert-butylperoxycarbonyl)pentyl radical (7a).

Item Type: Article
Journal or Publication Title: Magnetic Resonance in Chemistry
Uncontrolled Keywords: ESR spectroscopy ; radicals ; reaction mechanisms ; peroxides ; spin trap
Subjects: G Geography. Anthropology. Recreation > GE Environmental Sciences
Departments: Faculty of Science and Technology > Lancaster Environment Centre
ID Code: 21641
Deposited By: ep_ss_importer
Deposited On: 23 Jan 2009 09:27
Refereed?: Yes
Published?: Published
Last Modified: 26 Jul 2012 15:49
Identification Number:
URI: http://eprints.lancs.ac.uk/id/eprint/21641

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