Bulletin of the Korean chemical society | |
Correlation of the Rates of Solvolysis of Diphenylthiophosphinyl Chloride Using an Extended form of the Grunwald-Winstein Equation | |
Han Joong Koh1  Suk Jin Kang1  Dennis N Kevill1  | |
关键词: Diphenylthiophosphinyl chloride; Extended Grunwald-Winstein equation; SN2 pathway; | |
DOI : | |
学科分类:化学(综合) | |
来源: Korean Chemical Society | |
【 摘 要 】
Rate of solvolysis of diphenylthiophosphinyl chloride in ethanol, methanol, and aqueous binary mixtures incorporating ethanol, methanol, acetone, 2,2,2-trifluoroethanol (TFE) or 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) are reported. Solvolyses were also carried out in TFE-ethanol mixtures. For five representative solvents, studies were made at several temperatures and activation parameters determined. The 29 solvents gave a reasonably precise extended Grunwald-Winstein equation plot, correlation coefficient (R) of 0.933, which improved to 0.983 when the four TFE-ethanol points were excluded. The sensitivities (l = 1.00 and m = 0.64) were similar to those obtained for dimethyl phosphorochloridate and phosphorochloridothionate and diphenylphosphinyl chloride (1). As with the four previously studied solvolyses, an SN2 pathway is proposed for the solvolyses of diphenylthiophosphinyl chloride. The activation parameters, ツH× and ツS×, were determined and they are also in line with values expected for an SN2 reaction.
【 授权许可】
Unknown
【 预 览 】
Files | Size | Format | View |
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RO201912010240728ZK.pdf | 283KB | download |