Electron paramagnetic resonance spectroscopic study of the radicals formed during the photodecomposition of some bis(alkenoyl) peroxides, a bis(alkenoyl) peroxide and some peroxydicarbonates

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DOIResolve DOI: http://doi.org/10.1039/P29900001997
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TypeArticle
Journal titleJournal of the Chemical Society, Perkin Transactions 2
ISSN1472-779X
Issue11
Pages19972007; # of pages: 11
AbstractPhotolysis, at low temperatures in cyclopropane and/or CFCl 3, of bis[(E)-4,4-dimethylpent-2-enoyl]-peroxide 1, bis(4,4-dimethylpent-2-ynoyl) peroxide 2 and dipropyl peroxydicarbonate 3 yielded the corresponding carbonyloxyl radicals, viz. Me 3CCH=CHC(O)O ., Me 3CC≡CC(O)O . and PrOC(O)O ., which were identified by EPR spectroscopy. Carbonyloxyl radicals were not detected on photolysis of bis(3-methylbut-2-enoyl) peroxide 4, di[(E)-cinnamoyl] peroxide 7, and bis(1-methylpropyl) peroxydicarbonate 9. All the peroxides also give other radicals many of which were identified from their EPR spectral parameters. Thus, the two bis(alkenoyl) peroxides give the 'corresponding' alkenylacyl radicals, viz. s-cis- and s-trans-Me 3CCH=CHĊ=O from 1 and s-trans-Me 2C=CHĊ=O from compound 2. Evidence is presented which indicates that these acyl radicals may be formed directly during the photolysis of substrates 1 and 4 via a Norrish type-1 process. This would represent a new route for the photodecomposition of acyl peroxides with C-O bond scission occurring in competition with the usual O-O bond scission.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada (NRC-CNRC)
Peer reviewedYes
NPARC number21276668
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Record identifierd18bd0b3-c38d-47c3-b4e2-9a4e2e722be3
Record created2015-10-13
Record modified2016-05-09
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