112520-70-4Relevant articles and documents
Kinetics and mechanism of the aminolysis of aryl phenyl chlorothiophosphates with anilines
Ul Hoque, Md. Ehtesham,Dey, Shuchismita,Guha, Arun Kanti,Chan, Kyung Kim,Lee, Bon-Su,Hai, Whang Lee
, p. 5493 - 5499 (2007)
(Chemical Equation Presented) Kinetic studies of the reactions of aryl phenyl chlorothiophosphates (1) and aryl 4-chlorophenyl chlorothiophosphates (2) with substituted anilines in acetonitrile at 55.0°C are reported. The negative values of the cross-interaction constant ρXY (ρXY = -0.22 and -0.50 for 1 and 2, respectively) between substituents in the nucleophile (X) and substrate (Y) indicate that the reactions proceed by concerted SN2 mechanism. The primary kinetic isotope effects (kH/kD = 1.11-1.13 and 1.10-1.46 for 1 and 2, respectively) involving deuterated aniline nucleophiles are obtained. Front- and back-side nucleophilic attack on the substrates is proposed mainly on the basis of the primary kinetic isotope effects. A hydrogen-bonded, four-center-type transition state is suggested for a front-side attack, while the trigonal bipyramidal pentacoordinate transition state is suggested for a back-side attack. The MO theoretical calculations of the model reactions of dimethyl chlorothiophosphate (1′) and dimethyl chlorophosphate (3′) with ammonia are carried out. Considering the specific solvation effect, the front-side nucleophilic attack can occur competitively with the back-side attack in the reaction of 1′.
Kinetics and mechanism of the aminolysis of aryl ethyl chloro and chlorothio phosphates with anilines
Hoque, Md. Ehtesham Ul,Dey, Nilay Kumar,Kim, Chan Kyung,Lee, Bon-Su,Lee, Hai Whang
, p. 3944 - 3950 (2008/09/21)
The reactions of ethyl Y-phenyl chloro (1) and chlorothio (2) phosphates with X-anilines in acetonitrile at 55.0 °C are studied kinetically and theoretically. Kinetic results yield the primary kinetic isotope effects (k H/kD = 1.07-1.80 and 1.06-1.27 for 1 and 2, respectively) with deuterated aniline (XC6H4ND2) nucleophiles, and the cross-interaction constants ρXY = -0.60 and -0.28 for 1 and 2, respectively. A concerted mechanism involving a partial frontside attack through a hydrogen-bonded, four-center-type transition state is proposed. The large ρX (ρnuc = -3.1 to -3.4) and βX (βnuc = 1.1-1.2) values seem to be characteristic of the anilinolysis of phosphates and thiophosphates with the Cl leaving group. Because of the relatively large size of the aniline nucleophile, the degree of steric hindrance could be the decisive factor that determines the direction of the nucleophilic attack to the phosphate and thiophosphate substrates with the relatively small-sized Cl leaving group. This journal is The Royal Society of Chemistry.