Kinetic studies of solvent and pressure effects on thermochromic behavior of 6-nitrospiropyran.
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概要
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The thermal conversion of 6-nitrospiropyran from a merocyanine form to a spiro form was studied in various solvents and under high pressures. The rates of the thermal conversions were remarkably retarded in polar solvents, and a Kirkwood plot of the rate constants showed a large downward deviation as the solvent polarity increased. The rate constants (on a logarithmic scale) were linearly related to Kosower's <I>Z</I>-values. The values of the activation volumes were positive and divided into two groups: Δ<I>V</I><SUP>≠</SUP>≈10 cm<SUP>3</SUP> mol<SUP>−1</SUP> (in nonpolar solvents) and Δ<I>V</I><SUP>≠</SUP>≈20 cm<SUP>3</SUP> mol<SUP>−1</SUP> (in polar solvents). These findings suggest that for the reaction in polar solvents, specific interactions are operating and that the thermal conversion proceeds <I>via</I> a transition state which is much less polar than the initial 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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Ohcho Masanobu
Department of Chemistry, School of Science, Okayama University
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