Studies of the Thiocarbonyl Compounds. III. The Mechanism of the Thermal Rearrangement of Aryl Thionocarboxylates
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概要
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The thermal rearrangement of aryl thionocarboxylates was kinetically investigated in diphenyl ether. The rate constants of the rearrangement of aryl <I>N</I>,<I>N</I>-dimethylthionocarbamates were well correlated with the σ<SUP>−</SUP> values, but the plots of the electron-releasing <I>para</I>-substituents deviated slightly on the lower side of the <I>meta</I> correlation line. A good linear free-energy relationship existed between the rearrangement of aryl <I>N</I>,<I>N</I>-dimethylthionocarbamates and the bimolecular nucleophilic reaction of 4- or 5-substituted 1-chloro-2-nitrobenzenes with piperidine. By the use of the substituent constants obtained from the latter reaction for the electron-releasing <I>para</I>-substituent constants, a fairly good ρ–σ<SUP>−</SUP> relationship was obtained. Linear free-energy relationships also existed between the rearrangements of aryl <I>N</I>,<I>N</I>-dimethylthionocarbamates and aryl thionobenzoates, and between the rearrangements of aryl <I>N</I>,<I>N</I>-dimethylthionocarbamates and <I>O</I>-aryl <I>S</I>-phenyl dithiocarbonates. The order of the reaction constants was in accord with that of the inductive effects of the α-substituents of the thiocarbonyl group, so the electron-releasing conjugative effects of the α-substituents of the thiocarbonyl group did not play important roles in the rate-determining step. The present results indicate that the thermal rearrangement of aryl thionocarboxylates is an intramolecular S<SUB>N</SUB>–Ar which involves a four-membered cyclic transition state formed by a nucleophilic attack of the lone-pair electrons of the thiocarbonyl sulfur atom on the migrating aromatic ring.
- 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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Miyazaki Koshin
Chemical Research Laboratory, Nippon Soda Co., Ltd.
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