The One-electron Reduction of Carbonium Ions. VI. The Trapping of the Cycloheptatrienyl Radical with 2-Methyl-2-nitrosopropane in the Course of the Zinc Reduction of the Tropylium Ion

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概要

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• The zinc reduction of the tropylium ion was carried out in the presence of 2-methyl-2-nitrosopropane (a radical scavenger) in H<SUB>2</SUB>O–THF (7:3 by volume) at room temperature. In the reaction mixture with a short reaction time (5 min), <I>t</I>-butyl tropyl nitroxide (II) (a radical-trapping product) was identified by the ESR analysis. α-Phenyl-<I>N</I>-<I>t</I>-butylnitrone (I), which was isolated from the reaction mixture during a prolonged reaction time (30 min), was proved to be derived from the nitroxide II through the hydrogen abstraction by <I>t</I>-butyl nitroxide, which was itself formed from 2-methyl-2-nitrosopropane <I>in situ</I> in the acidic reaction mixture in the presence of zinc powder. The hydrogenation (on Pd/C) of the product mixture for a short reaction time (1 min) gave <I>N</I>-<I>t</I>-butyl-<I>N</I>-cycloheptylhydroxylamine and bicycloheptyl. On the basis of these observations, it is concluded that the primary product of the zinc reduction of the tropylium ion must be the tropyl radical.

• 公益社団法人 日本化学会の論文

著者

• Komatsu Koichi

  Department Of Environmental And Biological Chemistry Fukui University Of Technology

• Okamoto Kunio

  Department of Fuel Chemistry Faculty of Engineering Kyoto University

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