Kinetics and Mechanism of the Anilinolysis of Aryl Phenyl Chlorothiophosphates in Acetonitrile

Hai Whang Lee 1Chan Kyung Kim Bon-Su Lee Ehtesham U. Hoque Shuchismita Dey 

1. Inha University, Dept of Chem, 253 Yonghyundong, Incheon 402-751, Korea, South

Abstract

The kinetics and mechanism of the aminolysis of aryl phenyl chlorothiophosphates with anilines are investigated in acetonitrile at 55.0° C . A variation of ρY(δρY) with the change of substituent on the nucleophile (δσX) leads to a negative cross-interaction constant, ρXY = (δρY)/(δσX) = -0.2 while a large negative value, ρXY = -1.31, was observed for the anilinolysis of aryl phenyl chlorophosphates. The primary kinetic isotope effects with deuterated aniline nucleophiles are observed (kH/kD = 1.11-1.34) in contrast to the inverse secondary kinetic isotope effects (kH/kD = 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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Presentation: oral at 18th Conference on Physical Organic Chemistry, Symposium 2, by Hai Whang Lee
See On-line Journal of 18th Conference on Physical Organic Chemistry

Submitted: 2006-05-30 02:01
Revised:   2009-06-07 00:44
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