The Hofmann Rearrangement. II. Kinetic Substituent Effects of <I>ortho</I>-, <I>meta</I>-, and <I>para</I>-Substituted <I>N</I>-Chlorobenzamides

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概要

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• The reaction rates of the Hofmann rearrangement of <I>ortho</I>-, <I>meta</I>-, and <I>para</I>-substituted <I>N</I>-chlorobenzamides were measured under the same reaction conditions as were used for the preceding <I>N</I>-bromo series. The rate constants of the <I>N</I>-chloroamides were found to be slightly larger than those of the <I>N</I>-bromoamides. The relative values of the activation entropy and the activation enthalpy of <I>N</I>-chloro- and <I>N</I>-bromo-derivatives were approximately −4 e.u. and −1.3 kcal/mol respectively. The LFER between the two series was excellent, indicating that the reaction mechanism was almost the same for both series. The effects of the leaving group on the reactivity of <I>ortho</I>-substituents were discussed in terms of the <I>ortho</I>/<I>para</I> rate ratios and the relative values of the activation parameters of <I>ortho</I>- and <I>para</I>-substituents.

• 公益社団法人 日本化学会の論文

著者

• TSUNO Yuho

  The Institute for Fundamental Research of Organic Chemistry, Kyushu University

• Imamoto Tsuneo

  The Institute of Scientific and Industrial Research, Osaka University

• Yukawa Yasuhide

  The Institute of Scientific and Industrial Research, Osaka University

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