Kinetics and Mechanism of the Nucleophilic Substitution Reactions at Phosphorus Center

초록

The reactions of aryl phenyl chlorothiphosphates with anilines in acetonitile 55℃ ? proceed through concerted process and rates much slower than the corresponding reactions of its P=O analogue. A concerted process for less more basic anilines to a stepwise process with rate-limiting expulsion of leaving group for less basic anilines found in the aminolysis of aryl methyl phosphonochloridothioates with anilines in acetonitrile at 550.0 ?. The pyridinolysis of N-aryl-P,P-diphenyl phosphinic amides has been carries out in dimethyl sulfoxide at 85.0 ?. Both the Hammett plots show positive devation of two substituents 4-CH3CO and 4-CN. The cross-interaction constants are indicative of a concerted process.