Structure and Reactivity of Organic Ions in Gas-Phase Radiolysis. III. The Benzenonium Ions Formed by the Reactions of CH<SUB>5</SUB><SUP>+</SUP> and C<SUB>2</SUB>H<SUB>5</SUB><SUP>+</SUP> Ions from Methane with <I>o</I>-Xylene
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概要
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The gas-phase radiolysis of mixtures of <I>o</I>-xylene and excess methane has been studied at room temperature as a function of methane pressure and the added NO and NH<SUB>3</SUB> in order to investigate the reactions of CH<SUB>5</SUB><SUP>+</SUP> and C<SUB>2</SUB>H<SUB>5</SUB><SUP>+</SUP> ions from methane with <I>o</I>-xylene. It has been suggested that the proton transfers from these ions to <I>o</I>-xylene result in the isomerization to <I>m</I>-xylene <I>via</I> an intermediate σ complex, dimethylbenzenonium ion, and that a part of the C<SUB>2</SUB>H<SUB>5</SUB><SUP>+</SUP> ions is added to <I>o</I>-xylene leading to the formation of two isomers of dimethylethylbenzene. The proposed mechanism of the methane-sensitized isomerization of <I>o</I>-xylene to meta isomer has been supported by the observation that both <I>m</I>-xylene-<I>d</I><SUB>0</SUB> and <I>m</I>-xylene-<I>d</I><SUB>1</SUB> were formed in the radiolysis of a mixture of <I>o</I>-xylene and methane-<I>d</I><SUB>4</SUB>. The isotope effect (<I>k</I><SUB>H</SUB>/<I>k</I><SUB>D</SUB>) on the proton loss from the dimethylbenzenonium ion was roughly estimated to be 1.8±0.4. Group migration of intermediate a complexes was discussed.
- 公益社団法人 日本化学会の論文
著者
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Takamuku Setsuo
The Radiation Laboratory, The Institute of Scientific and Industrial Research, Osaka University
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Yamamoto Yukio
The Radiation Laboratory, The Institute of Scientific and Industrial Research, Osaka University
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Sakurai Hiroshi
The Radiation Laboratory, The Institute of Scientific and Industrial Research, Osaka University
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