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DOI: 10.1039/A809704F (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 2, 1999, 765-770

Kinetics and mechanism of the aminolysis of phenyl substituted phenyl chlorophosphates with anilines in acetonitrile

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Arun Kanti Guha, Hai Whang Lee and Ikchoon Lee

Abstract

The kinetics and mechanism of the aminolysis of phenyl substituted phenyl chlorophosphates with anilines are investigated in acetonitrile at 55.0 °C. Very sensitive variation of ρY (δρY [double greater-than, compressed] 0) with the change of substituent on the nucleophile (δσX) leads to a large negative cross-interaction constant, ρXY = (δρY)/(δσX) = –1.31. The secondary kinetic isotope effects observed with deuterated aniline nucleophiles are of the inverse type (kH[hair space]/kD = 0.61–0.87), and small ΔH[hair space] ‡ (1.6–9.7 kcal mol–1) and large negative ΔS[hair space] ‡ (–43 to –65 e.u.) values are obtained. These results are consistent with a concerted process with a late, product-like transition state in which both bond making and leaving group departure are extensive.

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