91638-90-3Relevant academic research and scientific papers
Kinetics and mechanism of the anilinolysis of dipropyl chlorophosphate in acetonitrile
Hoque, Md. Ehtesham Ul,Lee, Hai Whang
scheme or table, p. 1879 - 1884 (2012/07/31)
The kinetic studies on the reactions of dipropyl chlorophosphate (3O) with substituted anilines (XC6H4NH2) and deuterated anilines (XC6H4ND2) have been carried out in acetonitrile at 55.0 °C. The obtained deuterium kinetic isotope effects (DKIEs; kH/kD) are primary normal (kH/k D = 1.09-1.01) with the strongly basic anilines while secondary inverse (kH/kD = 0.74-0.82) with the weakly basic anilines. The steric effects of the two ligands on the rates are extensively discussed for the anilinolyses of the (R1O)(R2O)P(=O or S)Cl-type chlorophosphates and chlorothiophosphates. A concerted mechanism is proposed with a frontside nucleophilic attack involving a hydrogen-bonded four-center-type transition state for the strongly basic anilines and with a backside attack transition state for the weakly basic anilines on the basis of the DKIEs, primary normal and secondary inverse with the strongly and weakly basic anilines, respectively.
