38945-85-6Relevant articles and documents
Kinetics and mechanism of anilinolyses of aryl methyl and aryl propyl chlorothiophosphates in acetonitrile
Barai, Hasi Rani,Lee, Hai Whang
, p. 2797 - 2802 (2015/04/22)
Nucleophilic substitution reactions of Y-aryl methyl (8) and Y-aryl propyl (10) chlorothiophosphates with substituted anilines and deuterated anilines are investigated kinetically in acetonitrile at 55.0 °C. A concerted mechanism is proposed for 8 based o
Kinetics and mechanism of anilinolyses of ethyl methyl, ethyl propyl and diisopropyl chlorothiophosphates in acetonitrile
Barai, Hasi Rani,Hoque, Ehtesham Ul,Lee, Hai Whang
, p. 3811 - 3816 (2014/01/17)
Nucleophilic substitution reactions of ethyl methyl (2), ethyl propyl (4) and diisopropyl (7) chlorothiophosphates with substituted anilines and deuterated anilines are investigated kinetically in acetonitrile at 55.0 oC. A concerted mechanism is proposed based on the selectivity parameters. The deuterium kinetic isotope effects (DKIEs; kH/kD) are secondary inverse (kH/kD = 0.66-0.99) with 2, primary normal and secondary inverse (kH/ kD = 0.78-1.19) with 4, and primary normal (kH/kD = 1.06-1.21) with 7. The primary normal and secondary inverse DKIEs are rationalized by frontside attack involving hydrogen bonded, four-center-type transitionstate, and backside attack involving in-line-type transition state, respectively. The anilinolyses of ten chlorothiophosphates are examined based on the reactivity, steric effect of the two ligands, thio effect, reactionmechanism, DKIE and activation parameter.
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.