Reaction Mechanism Studies of Solvolytic Displacement of Chloride from Phosphorus

Abstract

The extended Grunwald-Winstein equation is applied to solvolytic displacement at phosphorus. Previous studies of the solvolyses of phosphorochloridates (RO)₂POCl, Ph₂POCl and [(CH₃)₂N]₂POCl are extended to cyclic phosphorochloridates, with five and six membered rings. Both kinetic and product ratio measurements are made. The equation is also applied to kinetic studies of the solvolyses of Ph₂PCl. The l and m sensitivity values are compared with previous values and with values for attack at sulfur, to give useful mechanistic information.

Keywords:

• Chlorodiphenylphosphine
• cyclic phosphorochloridates
• extended Grunwald-Winstein equation
• solvolysis

Acknowledgments

H.J.K thanks Chonju National University of Education for the granting of a sabbatical leave during the time that a portion of this research was performed. Acknowledgement made to the donors of the Petroleum Research Fund, administered by the American Chemical Society, for partial support of this research.

Notes

^a Number of data points;

^b from Eq. (1);

^c correlation coefficient;

^d from Ref. 7;

^e from Ref. 8.

^a From ref. 6;

^b this Work;

^c extrapolated using 3 or 4 values determined at higher temperatures.

^a From Eq. (3);

^b E, M, T represent ethanol, methanol, and TFE, with its percentage component given (remainder water); ethanol-water and methanol-water on volume-volume basis at 25.0°C and TFE-water on weight-weight basis;

^{c c} at 25.0°C.