Bulletin of the Korean chemical society | |
Application of the Extended Grunwald-Winstein Equation to the Solvolyses of Phenyl Methanesulfonyl Chloride in Aqueous Binary Mixtures | |
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
【 预 览 】
Files | Size | Format | View |
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RO201912010243010ZK.pdf | 229KB | download |