The mechanistic study of the hydroxyl radical reaction with trans-2-chlorovinyldichloroarsine

Abstract

The trans-2-chlorovinyldichloroarsine (Lewisite) was produced and handled during WWI and WWII as chemical warfare agents. It was very difficult to explore its chemical characterization by experiments ways. The quantum chemical calculations proved to be a precise and harmless method for the toxicological system. In this paper, the gas phase reaction mechanisms of OH radical with trans-2-chlorovinyldichloroarsine (lewisite) were studied by second-order Møller-Plesset perturbation theory (MP2) method. The geometries of reactants, products, complexes, and transition states were optimized at the MP2/6-311++G(d,p) level. To gain more accurate mechanistic knowledge, the single-point energies were calculated using G3 and CCSD(T) method. This reaction exhibited three mechanisms, namely, direct hydrogen abstraction, direct chlorine abstraction, and addition/elimination. Multichannel Rice-Ramsperger-Kassel-Marcus theory and transition-state theory have been carried out for overall and individual rate constants over a wide range of temperatures and pressures. The computational results indicated that addition/elimination reaction is more favorable than direct hydrogen abstraction and direct chlorine abstraction. The major products for the total reaction are AsCl2 and CHClCH2O generated via C(2)-addition/elimination.

Organocatalytic Asymmetric Epoxidation and Aziridination of Olefins and Their Synthetic Applications

“…330 Shi and co-workers showed that cis-1-propenylphosphoric acid potassium salt (735) could be epoxidized in 100% conversion and 74% ee using amine catalyst 737 and H 2 O 2 −CH 3 CN (Scheme 141). 331,332…”

“…It was believed that the electronegative fluorine atom may stabilize ammonium salts through hydrogen bonding and charge–dipole interactions (Figure ), which was beneficial for the catalytic efficiency . Shi and co-workers showed that cis -1-propenylphosphoric acid potassium salt ( 735 ) could be epoxidized in 100% conversion and 74% ee using amine catalyst 737 and H 2 O 2 –CH 3 CN (Scheme ). , …”

Study of Interaction between Human Hemoglobin and Antitubercular Isoniazid Drug with Its Detection

“…UV–vis absorption measurement is a common method to explore the structural change and acquire information of the complex formation . Figure shows UV–vis absorption spectra of HHb in the absence and presence of INH drug indicating a strong band in near‐UV region with a maximum 275 nm, which appears due to phenyl group of tryptophan (Trp) and tyrosine (Tyr) residues and another peak at 407 nm corresponds to the typical absorption of porphyrin‐soret band of HHb originated from heme groups, surrounded in a hydrophobic sack formed by the protein backbone through appropriate folding . The absorption peak at 275 nm of HHb‐INH system designates a slight shift toward shorter wavelength.…”

Kinetic modeling of the thermal destruction of lewisite

“…They found that the main detoxification reaction involves the breaking of a As-Cl bond to form a new As-S bond producing a non-toxic stable species (2-methyl-1,3,2-dithio arsolan-4-yl methanol). Zhang et al(Zhang et al, 2014) investigated theoretically the reaction of OH radicals with lewisite. The reactions envisaged involved H and Cl-atom abstractions as well as an addition followed by an atom elimination.…”