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18744390152
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For alkoxyl radicals bearing a single phenyl substituent such as the benzyloxyl and cumyloxyl radicals, aryl migration would lead to carbon-centered radicals that are significantly less stable than those formed from both the 1,1-diphenylethoxyl and triphenylmethoxyl radicals. Accordingly, with the former radicals the 1,2-phenyl shift does not compete with hydrogen atom abstraction, and β-fragmentation reactions.
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6
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18744400636
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2-saturated MeCN solution at 230 K, the peroxyl radical is described to be formed by oxygen quenching of either the bridged radical or the rearranged 1-phenoxy-1- phenylethyl radical. However, due to the very short lifetime suggested for the former radical (see ref 5), quenching of this radical by traces of oxygen is expected to be slower than the formation of the 1-phenoxy-1-phenylethyl radical. As a consequence, the peroxyl radical (if formed) is likely to derive from the reaction of this radical with oxygen.
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No evidence for the formation of phenols was obtained in the product analysis experiments.
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18744399121
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note
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According to this picture, the observation that the rate constants for β-scission of ring-substituted cumyloxyl radicals are essentially independent from the nature of the substituent (see ref 22) may indicate that substituent effects operate in the same direction on both the cumyloxyl radical and the product acetophenone.
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38
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18744381414
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Ar BDE in the 1,1-diaryalkoxyl radicals determined by the presence of ring substituents should not be important.
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