Application of the Extended Grunwald-Winstein Equation to the Solvolyses of Phenyl Methanesulfonyl Chloride in Aqueous Binary Mixtures

Bulletin of the Korean chemical society

Han Joong Koh Suk Jin Kang¹ 

关键词: Solvolyses for phenyl methanesulfonyl chloride;    Extended grunwald-winstein equation;    SN2 pathway;    Kinetic solvent isotope effect;   

DOI  :  

学科分类：化学（综合）

来源: Korean Chemical Society

【 摘 要 】

This report shows the rates of solvolyses for phenyl methanesulfonyl chloride (C6H5CH2SO2Cl, I) in ethanol, methanol, and aqueous binary mixtures incorporating ethanol, methanol, acetone, 2,2,2-trifluroethanol (TFE) and 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) are reported. Three representative solvents, studies were made at several temperatures and activation parameters were determined. The thirty kinds of solvents gave a reasonably precise extended Grunwald-Winstein plot, coefficient (R) of 0.954. The sensitivity values (l = 0.61 and m = 0.34, l/m = 1.8) of phenyl methanesulfonyl chloride (I) were smaller than those obtained for benzenesulfonyl chloride (C6H5SO2Cl, II; l = 1.01 and m = 0.61) and 2-propanesulfonyl chloride ((CH3)2CHSO2Cl, III; l = 1.28 and m = 0.64). As with the two previously studied solvolyses, an SN2 pathway with somewhat ionization reaction is proposed for the solvolyses of I. The activation parameters, ΔH≠ and ΔS≠, were determined and they are also in line with values expected for a bimolecular reaction mechanism. The kinetic solvent isotope effect of 2.34 in CH3OH/CH3OD is in accord with a bimolecular mechanism, probably assisted by general-base catalysis.

【 授权许可】

Unknown