- 作者: 劉廣定
- 作者服務機構: 台灣大學化學系
- 中文摘要: The results of detailed examinations on the comparison of Hammett-type correlation analysis of solvolytic rate constants with single- and dual-parameter equations are summarized. From the difference of .rho. values, the variation of .gamma. values with numbers of data points, the solvent intervention in the standard reactions for defining .sigma./sup +/ constants, the influence of o-methyl group on the reactivity of the reference substrate (tert-cumyl derivatives), and the behavior of the . alpha.-aryl group in highly congested systems, it could be concluded that both the Hammett-Brown and the Yukawa-Tsuno treatments of solvolytic rate constants are only approximations. Although in some cases the use of the dual-parameter Yukawa-Tsuno equation could give a better correlation and a more proper explanation than the use of the single-parameter Hammett-Brown equation, in other cases the excellent correlation observed from the former might be merely a computational artefact. Therefore, the result obtained from the Yukawa-Tsuno equation should be interpreted with caution.
- 英文摘要: --
- 中文關鍵字: Solvolysis Rate; Kinetic Isotope Effect; Solvent Effect; Hammett Type Correlation Analysis; Tertiary Benzylic Derivative
- 英文關鍵字: 溶離速率;動力學同位素效應;溶劑效應;哈曼特型相關分析;三級苯甲基衍生物