Kinetic analysis of the high-pressure Diels-Alder reactions of tropone with maleic anhydride and norbornene.
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概要
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The kinetics of Diels-Alder reactions of tropone with maleic anhydride and norbornene were studied at pressures up to 2000 bar. The activation volumes, obtained from the former at 378.2 K in isopropylbenzene (IPB) and <I>N</I>,<I>N</I>-dimethylformamide (DMF), were Δ<I>V</I><SUP>≠</SUP>(IPB)=−21.4 cm<SUP>3</SUP>/mol and Δ<I>V</I><SUP>≠</SUP>(DMP)=−16.8 cm<SUP>3</SUP>/mol. Those from the latter (at 408.2 K) were Δ<I>V</I><SUP>≠</SUP>(IPB)=−30.0 cm<SUP>3</SUP>/mol and Δ<I>V</I><SUP>≠</SUP>(DMF)=−27.8 cm<SUP>3</SUP>/mol. These Δ<I>V</I><SUP>≠</SUP> and Δ<I>V</I> showed a large deviation from those of the (6+4)π process of tropone with cyclopentadiene (by le Noble) and a small deviation from those of other typical Diels-Alder reactions to support the concerted cycloaddition mechanism which has been established by the kinetic analysis at atmospheric pressure.
- 公益社団法人 日本化学会の論文
著者
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Takeshita Hitoshi
Research Institute of Industrial Science, 86, Kyushu University
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Hatsui Toshihide
Research Institute of Industrial Science, 86, Kyushu University
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Sugiyama Shigeru
Research Institute of Industrial Science, 86, Kyushu University
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