Kinetic applications of electron paramagnetic resonance spectroscopy. 30. Rearrangement of the benzoylmethyl radical

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DOIResolve DOI: http://doi.org/10.1021/ja00455a038
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TypeArticle
Journal titleJournal of the American Chemical Society
ISSN0002-7863
Volume99
Issue13
Pages44474450; # of pages: 4
AbstractThe EPR spectra of benzoylmethyl, 1-benzoylethyl, and 2-benzoyl-2-propyl radicals in solution are reported. Barriers to rotation about the C(O)-ĊH2 and C(O)-ĊMe2 bonds have been measured. At low temperatures, benzoylmethyl radicals dimerize at rates close to the diffusion-controlled limit. At high temperatures decay occurs by a neophyl-like rearrangement and the benzyl radical is observed because the initially produced phenylacetyl radical is rapidly decarbonylated. The coresponding rearrangements of the 1-benzoylethyl and 2-benzoyl-2-propyl radicals are much slower than that of the benzoylmethyl radical at comparable temperatures. The results of kinetic studies on these dimerization, isomerization, and decarbonylation reactions are discussed in relation to the failure of early attempts4 to obtain 1,4-diketones by dehydrodimerization of alkyl phenyl ketones.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada (NRC-CNRC)
Peer reviewedYes
NPARC number21276691
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Record identifier0e59d616-c2ff-4b12-8ef5-53d7a26ed15c
Record created2015-10-13
Record modified2016-05-09
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