The thermal cis-to-trans isomerization of N,N'-diacylindigos. Kinetic pressure, solvent, and substituent effects.
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概要
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The kinetics of the thermal <I>cis</I>-to-<I>trans</I> isomerization of <I>N</I>,<I>N</I>′-diacylindigos(DAI) in various solvents and under high pressures has been studied. <I>N</I>,<I>N</I>′-Dibenzoylindigos(DBI) isomerize about 10 times slower than molecules not having a benzene ring in the acyl groups. The values of the activation volumes were about 8.0 cm<SUP>3</SUP> mol<SUP>−1</SUP> for the former and about 3.0 cm<SUP>3</SUP> mol<SUP>−1</SUP> for the latter. It was suggested that the thermal isomerization proceeds <I>via</I> the biradical mechanism. The positive values of the activation volume have been interpreted in terms of the increase in the intrinsic volume upon activation. The differences in the isomerization rates and the activation parameters between DBI and the others have been ascribed to an additional interaction between the two phenyl rings in the acyl groups in the <I>cis</I>-ground state.
- 公益社団法人 日本化学会の論文
著者
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Sueishi Yoshimi
Department Of Chemistry Faculty Of Science Okayama University
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Nishimura Norio
Department Of Chemistry Faculty Of Science Okayama University
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Ohtani Kazuo
Department of Chemistry, School of Science, Okayama University
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