Solvent effects in the conversion of phenyldiazomethane into stilbene and spirooxetane in the reaction with chloranil.
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概要
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A stereochemical study was made of the reaction of phenyldiazomethane(<B>1</B>) with chloranil(<B>2</B>) at 20 °C in 28 aprotic solvents. The products were <I>trans</I>-spirooxetane(<B>4</B>) and <I>cis</I>-<I>trans</I> mixtures of stilbene(<B>3</B>) (<I>ca.</I> 2–5 times <I>cis</I>-rich). The molar ratios of <I>cis</I>-<B>3</B> to the sum of the <I>trans</I>-<B>3</B> and <B>4</B> tended to increase, whereas the <B>4</B> to <I>trans</I>-<B>3</B> ratios decrease with the increase in the solvent basicity and polarity. These effects of solvents on the product distributions were interpreted in terms of the effects of the solvent basicity and polarity on the stereoselective formation of the diazonium betaine intermediate and on the conformational isomerism. Moderately successful linear-free-energy(LFE) relationships were established for these product ratios with the aid of the combination of the empirical solvent basicity parameter, <I>D</I><SUB>π</SUB>, and the Kirkwood function, <I>f</I>(ε), or <I>E</I><SUB>T</SUB> values as the solvent polarity parameters.
- 公益社団法人 日本化学会の論文
著者
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Oshima Takumi
Institute Of Chemistry College Of General Education Osaka University
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Nagai Toshikazu
Institute Of Chemistry College Of General Education Osaka University
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Nishioka Ryoji
Institute of Chemistry, College of General Education, Osaka University
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