Kinetics and Mechanism of the Reaction of para-Chlorophenyl Aryl Chlorophosphates with Anilines in Acetonitrile

초록

The kinetics and mechanism of the nucleophilic substitution reactions of ρ-chlorophenyl aryl chlorophosphates (2) with anilines are investigated in acetonitrile at 55.0 ‘C. Relatively large magnitudes of ρx and βx values are indicative of a large degree of bond making in the TS. Smaller magnitudes of ρx (0.20 for X=H) and ρxy (-0.30) than those for the corresponding reactions with phenyl aryl chlorophosphates (1) (ρx = 0.54 for X=H and ρxy = -1.31) are interpreted to indicate partial electron loss, or shunt, towards the electron acceptor equatorial ligand (p-ClC6H4O-) in the biphyramidal pentacoordinated transition atate.