Studies of the Thiocarbonyl Compounds. II. Syntheses and Thermal Rearrangement of Aryl Thionobenzoates
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概要
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Various aryl thionobenzoates were prepared. When maintained at elevated temperatures, they rearranged smoothly to aryl thiolbenzoates. The mechanism of this rearrangement was kinetically investigated. The rearrangement rates were correlated with the first-order kinetic equation, and the rearrangement was found to be facilitated by substitution with an electron-withdrawing group in the migrating aromatic rings. The Hammett ρ value was found to be 2.11 in diphenyl ether at 200.5°C. The entropies of activation were negative. A linear free-energy relationship existed between this rearrangement and the rearrangement of <I>O</I>,<I>S</I>-diaryl dithiocarbonates. From these observations, a four-membered cyclic structure can be suggested as the transition state for this rearrangement. The present results indicate that the existence of hetero atoms directly bound to the thiocarbonyl group is not essential for the thermal rearrangement with intramolecular 1,3 aryl migration from oxygen to sulfur.
- 公益社団法人 日本化学会の論文
著者
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Kaji Aritsune
Department of Chemistry, Faculty of Science, Kyoto University
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Araki Yoshiaki
Department of Chemistry, Faculty of Science, Kyoto University
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