Bulletin of the Korean chemical society | |
A Kinetic Study on Solvolysis of Diphenyl Thiophosphorochloridate | |
Han Joong Koh1  Suk Jin Kang1  Dennis N Kevill1  | |
关键词: Diphenyl thiophosphorochloridate; Extended Grunwald-Winstein equation; SN2 mechanism; | |
DOI : | |
学科分类:化学(综合) | |
来源: Korean Chemical Society | |
【 摘 要 】
Rates of solvolyses of diphenyl thiophosphorochloridate ((PhO)2PSCl, 1) in ethanol, methanol, and aqueous binary mixtures incorporating ethanol, methanol, acetone and 2,2,2-trifluoroethanol (TFE) are reported. For four representative solvents, studies were made at several temperatures and activation parameters were determined. The 30 solvents gave a reasonably precise extended Grunwald-Winstein plot, correlation coefficient (R) of 0.989. The sensitivity values (l = 1.29 and m = 0.64) of diphenyl thiophosphorochloridate ((PhO)2PSCl, 1) were similar to those obtained for diphenyl phosphorochloridate ((PhO)2POCl, 2), diphenylphosphinyl chloride (Ph2POCl, 3) and diphenylthiophosphinyl chloride (Ph2PSCl, 4). As with the previously studied of 3~4 solvolyses, an SN2 pathway is proposed for the solvolyses of diphenyl thiophosphorochloridate (1). The activation parameters, ツH× (= 11.6~13.9 kcal?mol-1) and ツS× (= -32.1 ~ -42.7 cal?mol-1?K-1), were determined, and they were in line with values expected for an SN2 reaction. The large kinetic solvent isotope effects (KSIE, 2.44 in MeOH/MeOD and 3.46 in H2O/D2O) are also well explained by the proposed SN2 mechanism.
【 授权许可】
Unknown
【 预 览 】
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RO201912010241429ZK.pdf | 342KB | download |