Elimination and nucleophilic substitution on nitrogen atom. Reactions of -O-aroyl-N,N-di(p-substituted benzyl)- and O-aroyl-N-benzoyl-N-benzylhydroxylamines with various nucleophiles in dipolar aprotic solvents.

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概要

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• The reactions of the title compounds with various nucleophiles were found to proceed through either elimination or nucleophilic substitution on the nitrogen atom depending on both the structure of the substrate and the nature of nucleophiles used. The effect of substituent and the primary isotope effect (<I>k</I><SUB>H</SUB>⁄<I>k</I><SUB>D</SUB> of 7.6 and 8.1 with NaN<SUB>3</SUB> and LiCl at 30 °C) on the elimination of <I>O</I>-(<I>p</I>-nitrobenzoyl)-<I>N</I>,<I>N</I>-dibenzylhydroxylamine revealed that the reaction is an E2 process involving the rate-determining proton abstraction by base and proceeds <I>via</I> an ionic transition state of an ideal concerted type. Nucleophilic substitution on the trivalent nitrogen atom has been inferred for the reactions with such nucleophiles as diethyl sulfide, <I>p</I>-toluenethiol and sodium cyanide on the basis of product distribution.

• 公益社団法人 日本化学会の論文

著者

• Sakurai Tadamitsu

  Department Of Applied Chemistry Faculty Of Engineering Kanagawa University

• Oae Shigeru

  Deparment of Applied Chemistry Faculty of Engineering Osaka City University

• Sakurai Tadamitsu

  Department of Applied Chemistry, Faculty of Engineering, Osaka City University

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