The sulfuranyl radical structure and reactions of o-(thio)benzoyloxyl radicals formed by the decomposition of t-butyl o-(thio)-perbenzoates studied by 1H and 13C CIDNP and 17O NMR.
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概要
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<SUP>1</SUP>H and <SUP>13</SUP>C CIDNP signals were observed in the methyl group of <I>o</I>-(methylthio)benzoic acid and the methylene group of 3,1-benzoxathian-4-one (<B>6</B>) during the thermal decomposition of <I>t</I>-butyl <I>o</I>-(methylthio)perbenzoate. The results show that the free "<I>o</I>-(methylthio)benzoyloxyl radical" itself is better represented as the bridged sulfuranyl radical in which most of the spin density is localized at the sulfur atom rather than in the carboxyl. Thermolysis of <I>t</I>-butyl <I>o</I>-(methylthio)- and <I>o</I>-(phenylthio)perbenzoates-<I>carbonyl</I>-<SUP>17</SUP><I>O</I> was carried out and the oxygen labels were detected by <SUP>17</SUP>O NMR spectroscopy preferentially at the carbonyl oxygen of <B>6</B> and diphenyl 2,2′-dithiodibenzoate ruling out the zwitterionic radical structure. The migration of phenyl group and the peroxomonosulfate oxidation of <I>o</I>-(phenylthio)benzoic acid are also discussed.
- 公益社団法人 日本化学会の論文
著者
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Nakanishi Waro
Department Of Chemistry Faculty Of Education Wakayama University
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Kusuyama Yoshiaki
Department Of Chemistry Faculty Of Education Wakayama University
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Ikeda Yoshitsugu
Department of Chemistry, Faculty of Education, Wakayama University
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Iwamura Hiizu
Division of Applied Molecular Science, Institute for Molecular Science
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