Kinetics and mechanism of the reaction of para-chlorophenyl aryl chlorophosphates with anilines in acetonitrile
作者： Hai Whang Lee , Arun Kanti Guha , Ikchoon Lee
DOI: 10.1002/KIN.10081
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摘要: The kinetics and mechanism of the nucleophilic substitution reactions p-chlorophenyl aryl chlorophosphates (2) with anilines are investigated in acetonitrile at 55°C. Relatively large magnitudes ρX βX values indicative a degree bond making TS. Smaller (0.20 for X = H) ρXY (−0.30) than those corresponding phenyl (1) (ρX 0.54 H −1.31) interpreted to indicate partial electron loss, or shunt, towards acceptor equatorial ligand (p-ClC6H4O-) bipyramidal pentacoordinated transition state. inverse secondary kinetic isotope effects (kH/kD 0.64–0.87) involving deuterated aniline (ND2C6H4X) nucleophiles, small ΔH‡ negative ΔS‡ obtained. These results consistent concerted mechanism. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 632–637,
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