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

Specific 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.