Products and kinetic substituent effects in the reactions of diaryldiazomethanes with 2,5-dichloro-p-benzoquinone.
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概要
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Substituted diphenyldiazomethanes[(x-C<SUB>6</SUB>H<SUB>4</SUB>)<SUB>2</SUB>CN<SUB>2</SUB>; x=<I>p</I>-OCH<SUB>3</SUB>, <I>p</I>-CH<SUB>3</SUB>, H, <I>p</I>-Cl] were found to react with 2,5-dichloro-<I>p</I>-benzoquinone at its conjugated C=C and C=O bonds to give bicyclic diones and poly(2,5-dichlorohydroquinone benzhydryl ether)s respectively, obeying the second-order kinetic law. The product ratios of the polyethers to the bicyclic diones increased from 1.1 to 8.1 with the electron-donating ability of the substituents. The individual rate constants were well correlated with the Hammett equation: log<I>k</I><SUB>3</SUB>=−2.15–1.55 σ (<I>r</I>=0.996) and log<I>k</I><SUB>4</SUB>=−2.03–1.85 (σ<SUP>0</SUP>+0.515Δ\barσ<SUB>R</SUB><SUP>+</SUP>) (<I>r</I>=1.00) for the bicyclic diones and polyethers processes respectively. The presence of methanol as a trapping agent stopped the polymerization completely and afforded the methanolysis product, though no essential change was found in the formation of the bicyclic dione.
- 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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