The kinetics and mechanism of the aminolysis of aryl phenyl chlorothiophosphates with anilines are investigated in acetonitrile at 55.0° C . A variation of ρ_Y(δρ_Y) with the change of substituent on the nucleophile (δσ_X) leads to a negative cross-interaction constant, ρ_XY = (δρ_Y)/(δσ_X) = -0.2 while a large negative value, ρ_XY = -1.31, was observed for the anilinolysis of aryl phenyl chlorophosphates. The primary kinetic isotope effects with deuterated aniline nucleophiles are observed (k_H/k_D = 1.11-1.34) in contrast to the inverse secondary kinetic isotope effects (k_H/k_D = 0.61-0.87) of the anilinolysis of aryl phenyl chlorophosphates. These results and theoretical calculations are consistent with a concerted process with front side attack of nucleophile while a concerted process with a late, product-like transition state in which both bond making and leaving group departure are extensive in the anilinolysis of aryl phenyl chlorophosphates.

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