Further consideration of the correlation of the rates of solvolytic displacement of chloride ion from phosphorus (V)

Abstract

AbstractSpecific rates of solvolysis of diphenyl (1) and bis(2,4‐dichlorophenyl) (3) phosphorochloridate (chlorophosphate) have been determined by a conductivity technique. The available specific rates together with those determined earlier for bis(4‐chlorophenyl) phosphorochloridate (2) have been analyzed in terms of the extended (two‐term) Grunwald–Winstein equation. It is found that rather poor overall correlations found earlier for 1 and 2 and now for 3 are considerably improved when data points for 2,2,2‐trifluoroethanol–ethanol and acetone–water mixtures are excluded. The large sensitivities toward changes in solvent nucleophilicity are consistent with a bimolecular process. The differences in nucleophilicity of an acetone–water mixture for attack at carbon or at phosphorus are discussed. Copyright © 2010 John Wiley & Sons, Ltd.