17729-95-2Relevant academic research and scientific papers
Anilinolysis of O-butyl phenyl phosphonochloridothioate in acetonitrile: Synthesis, characterization, kinetic study, and reaction mechanism
Barai, Hasi Rani,Kim, Ji-Hoon,Joo, Sang Woo
, (2017)
This paper describes a simple optimized method for the synthesis of O-butyl phenyl phosphonochloridothioate (4) under mild conditions. The target compounds were characterized by 1H-nuclear magnetic resonance (NMR), 13C-NMR, and 31P-NMR spectroscopy, as well as mass spectroscopy. The apparent structure of 4 was confirmed by optimization using the B3LYP/6-311?+?G(d,p) level in the Gaussian 09 program in acetonitrile. The nucleophilic substitution reactions of 4 with X-anilines (XC6H4NH2) and deuterated X-anilines (XC6H4ND2) were investigated kinetically in acetonitrile at 55.0°C. The free energy relationship with X in the anilines looked biphasic concave upwards with a break region between X?=?H and X?=?3-MeO, giving large negative ρX and small positive βX values. The deuterium kinetic isotope effects were secondary inverse (kH/kD?H/kD), increased when the nucleophiles were changed from weakly basic to strongly basic anilines. A concerted SN2 mechanism is proposed on the basis of the selectivity parameters and the variation trend of the deuterium kinetic isotope effects with X.
