Reactions of 2,4,6-Tri-<I>t</I>-butylnitrosobenzene with Grignard Reagents

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概要

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• Reactions of 2,4,6-tri-<I>t</I>-butylnitrosobenzene (<B>1</B>) with alkylmagnesium halides afforded 6-alkyl-1-hydroxy-imino-2,4,6-tri-<I>t</I>-butyl-2,4-cyclohexadienes (<B>2</B>), 4-alkyl-1-hydroxyimino-2,4,6-tri-<I>t</I>-butyl-2,5-cyclohexadienes (<B>3</B>), and <I>N</I>-alkyl-2,4,6-tri-<I>t</I>-butylanilines (<B>4</B>) depending on the Grignard reagents used. The distribution of the reaction products indicated that the oximes were formed <I>via</I> an attack of the anionic species on the <I>ortho</I>- and the <I>para</I>-carbons, respectively, to the nitroso group, but that the <I>N</I>-alkylanilines <I>via</I> a free radical mechanism involving an electron transfer from the Grignard reagent to <B>1</B>. The free radical mechanism was confirmed in the case of <I>t</I>-butylmagnesium chloride by trapping the <I>t</I>-butyl radicals as 1-<I>t</I>-butoxyimino-2,4,4,6-tetra-<I>t</I>-butyl-2,5-cyclohexadiene (<B>8</B>). Such a mechanistic difference has been explained in terms of the difference in electron affinities of the free radicals derived from Grignard reagents.

• 公益社団法人 日本化学会の論文

著者

• Okazaki Renji

  Department Of Chemical And Biological Sciences Faculty Of Science Japan Women's University

• Inagaki Yoshio

  Department of Chemistry, Faculty of Science, The University of Tokyo

• Inamoto Naoki

  Department of Chemistry and Research Centre for Spectrochemistry, Faculty of Science, The University of Tokyo

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