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红外光谱中溶剂效应机理研究(Ⅳ) 溶剂受电子位阻效应常数的确定

Study on the Mechanism of the Solvent Effect of Infrared Spectra (Ⅳ)Determination of the Constants of Electron Acception Space Effect of Solvents

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【作者】 李润卿张捷陈惠明李玉荷徐效华谢庆兰

【Author】 Li Runqing; Zhang Jie; Chen Huiming; Li Yuhe (The Analytical Center of Tianjin University Tianjin, China, 300072)Xu Xiaohua; Xie Qinglan (National Key Laboratory of Elements-Organic Chemistry Nankai Univerity Tianjin, China,30071)

【机构】 天津大学分析中心!天津300072天津大学化学系天津300072南开大学元素有机化学国家重点实验室!天津300071

【Abstract】 In the previous paper(Ⅲ), the following equation of solvent effect in organic chemistry was suggested:Where Ei is a physical or chemical property of the substrate in the solvent i and E0 is that in n-hexane. Ai and Di are constants of electron acception and donation effect of the solvent i respectively. VAi and VDi are constants of electron acception and donation space effect of the solvent i respectively, a and d are the sensitivities of E of the substrate vs the change of Ai and Di. Va and Vd are the constants of electron acception and donation space effect of the substrate respectively. In IR spectra E couJd be substituted by the wavenumber (v). Ai and VAi have been estalished for 18 organic solvents (n-C6H14, n-C7H16, cyclohexane, CC14, Ph-Me, ClCH:CCl2, Et2O, CHCl3, C6H6, CH2Cl2,ClCH2 CH2Cl, Ph-NO2, THF, 1,4-dioxane, Et-NO2. MeCO2Et, Me-NO2, Me-CN).In this paper Di and VDi have been established for these solvents. The equation also has been tested by the vC-X (X=Cl, Br) of five alkylhalides (t-BuCl, ) n-C5H11Cl,t-BuBr, Et-Br, EtC(H)BrMe) and YC=O of three carboxyl compounds (t-BuCOMe,Me2CO, MHB) and seven organotin compounds [(Ph2MeSiCH2)3SnO2C-C6H4-X-p (X=H-, CH3-, CH3O-, NO2-, F-, Cl-, I-)].The relationship (u = ρ·σ + vo) between vC=O of organotin compounds and Hammett constants (σ) of the substituted groups in different solvents was studied and a relationship bewteen ρ and Ai, VAi ) Di, VDi of the slovents was found.

  • 【文献出处】 物理化学学报 ,Acta Physico-chimica Sinica , 编辑部邮箱 ,1995年09期
  • 【分类号】O621
  • 【被引频次】2
  • 【下载频次】117
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