ISSN:
0021-8383
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The decomposition of tert-butyl hydroperoxide by photochemically induced reactions in DMSOAbbreviations used: DMSO, dimethyl sulfoxide; DMSO-d6, completely deuterium labelled dimethyl sulfoxide; cw-ESR, continuous-wave Electron Spin Resonance; u. v., ultra violet; DMPO, 5, 5-dimethyl-I-pyrroline N-oxide; TMPO, 3, 3, 5, 5-tetramethyl-l-pyrroline N-oxide. and water was investigated by cw-e.s.r. spectroscopy. The products tert-butylperoxyl, methyl and sulfur-centered free radicals were identified. The tert-butoxyl free radical is involved in the primary process as shown by time-resolved e.s.r. technique. On the basis of directly identified radical species, a mechanism for the photochemically induced reactions of tert-butyl hydroperoxide in DMSO is proposed. At concentrations below 0.8 mol · l-1 the radical formation from tert-butyl hydroperoxide proceeds by cleavage of the O—O bond rather than by hydrogen abstraction.
Additional Material:
14 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/prac.19913330215
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