SN2 reactions in dipolar aprotic solvents. VIII. Chlorine isotopic exchange reaction of (arylsulfonyl)chloromethanes, (arylsulfinyl)chloromethanes, and 2-chloro-1-arylethanones in acetonitrile. A role of the nucleophile-substrate interaction in the Finkel
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概要
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Chlorine isotopic exchange reactions of substituted chloromethanes [(arylsulfonyl)chloromethanes (<B>1</B>), (arylsulfinyl)chloromethanes (<B>2</B>), and 2-chloro-1-arylethanones (<B>4</B>)] with tetraethylammonium chloride-<SUP>36</SUP>Cl were studied in acetonitrile. This study enabled, for the first time, the accurate rate study of the former two classes of compounds (<B>1</B> and <B>2</B>) of extremely low reactivity. Both the large enthalpies of activation and the positive entropies of activation were the characteristics for these two substrates (<B>1</B>-<I>p</I>-NO<SUB>2</SUB> and <B>2</B>-<I>p</I>-NO<SUB>2</SUB>). High reactivity of 2-chloro-1-phenylethanone was substantiated, and was not associated with the significant secondary kinetic deuterium isotope effect. A nucleophile-substrate association that proceeds the reaction was suggested and the possible role of such an interaction was examined in the light of the intermediary of the nucleophile-substrate complex in the Finkelstein reaction.
- 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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Hayami Jun-ichi
Department of Chemistry, Faculty of Science, Kyoto University
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Koyanagi Tohru
Department of Chemistry, Faculty of Science, Kyoto University
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