A Kinetic Study on Solvolysis of Diphenyl Thiophosphorochloridate

다국어 초록 (Multilingual Abstract)

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, ΔH≠ (= 11.6~13.9 kcal․mol-1) and ΔS≠ (= -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.

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