35749-93-0Relevant articles and documents
Concerted pathway to the mechanism of the Anilinolysis of Bis(N,N-diethylamino)phosphinic chloride in Acetonitrile
Barai, Hasi Rani
, p. 101 - 105 (2017/01/18)
The kinetics of the nucleophilic substitution reactions of bis(N,N-diethylamino)phosphinic chloride with substituted anilines (XC6H4NH2) and deuterated anilines (XC6H4ND2) are investigated in MeCN at 65.0°C. The deuterium kinetic isotope effects (DKIEs) are secondary inverse (kH/kD1: 0.706-0.947) and the magnitudes of the secondary inverse DKIEs (kH/kD) increase constantly as the nucleophiles are changed from weakly basic to strongly basic anilines. The magnitudes of the selectivity parameters are ρX(H)≤-6.34, and βX(H)≤2.24 with substituted anilines and ρX(D)≤-6.13 and βX(D)≤2.17 with deuterated anilines. A concerted SN2 mechanism involving predominant backside attack is proposed based on the kH/kD values with substituent X.
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.
Anilinolysis of diethyl isothiocyanophosphate in acetonitrile
Barai, Hasi Rani,Adhikary, Keshab Kumar,Lee, Hai Whang
experimental part, p. 1089 - 1092 (2012/05/05)
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