Effect of Pressure on the Rate of Solvolysis. Formolysis of 1-(<I>p</I>-Substituted benzyl)ethyl Tosylates

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概要

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• The effect of pressure on the formolysis of 1-(<I>P</I>-substituted benzyl) ethyl tosylates was investigated, and the activation volumes, <I>ΔV<SUB>o</SUB></I><SUP>\neweq</SUP> were estimated. The apparent values of activation volume were found to correlate nicely with σ<SUP>*</SUP>. Because the present substrates were believed to be formolyzed through two separate processes, anchimerically assisted (<I>k</I><SUB><I>Δ</I></SUB>) and unassisted (<I>k</I><SUB>s</SUB>), the apparent values of activation volume were partitioned into the corresponding activation volumes, <I>ΔV</I><SUB><I>Δ</I></SUB><SUP>\neweq</SUP> and <I>ΔV<SUB>s</SUB></I><SUP>\neweq</SUP>. The dependence of <I>ΔV</I><SUB><I>Δ</I></SUB><SUP>\neweq</SUP> and <I>ΔV<SUB>s</SUB></I><SUP>\neweq</SUP> on the substituents was examined, and the correlation between the mechanisms of solvolysis and <I>ΔV</I><SUB><I>Δ</I></SUB><SUP>\neweq</SUP> and <I>ΔV<SUB>s</SUB></I><SUP>\neweq</SUP> was discussed.

• 公益社団法人 日本化学会の論文

著者

• Maruyama Kazuhiro

  Department Of Chemistry Faculty Of Science Kyoto University

• Sera Akira

  Department Of Chemistry Faculty Of Science Kobe University

• Yamagami Chisako

  Department of Chemistry, Faculty of Science, Kyoto University

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