73077-18-6Relevant academic research and scientific papers
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.
