Tuning the Lewis acidity of metal–organic frameworks for enhanced catalysis

The kinetics of hydrolysis of dimethyl nitrophenyl phosphate (DMNP), a simulant of the nerve agent Soman, was studied and revealed transition metal salts as catalysts.

Synthesis, structure and reactivity of oxalyl di(4-methylimidazole)

The article describes a two-step method for the synthesis of oxalyl di(4-methylimidazole) from 4(5)-methylimidazole through 1-trimethyl-4-methylimidazole followed by interaction with oxalyl chloride; the yield of the final product is 89%. The kinetics of hydrolysis, alcoholysis, and aminolysis of oxalyl di(4-methylimidazole) in acetonitrile – water (9 : 1), acetonitrile – methanol (9 : 1), acetonitrile – diethylamine (9 : 1) at 25 °C was studied. To study the thermodynamic features of the reactions to obtain this compound in the Spartan’14 1.1.4 program, a number of thermodynamic characteristics were determined that determine the spontaneous and exothermic nature of the process. The data obtained make it possible to select the optimal conditions for the synthesis of oxalyl di(4-methylimidazole) and to draw a conclusion about its low stability in media containing nucleophiles. Possible conformers were found for the oxalyl di(4-methylimidazole) molecule in the Molecular Operating Environment 2014.0901 program, for which nucleophilic susceptibility surfaces were calculated in the SCIGRESS Modeling 3.1.4 program. It was shown that the most reactive conformers in which carbonyl groups are minimally screened by fragments of 4-methylimidazole. The structure of oxalyl di(4-methylimidazole) was confirmed by IR and 1H NMR spectroscopy. Characteristic absorption bands were found in the IR spectra, confirming the presence of the corresponding functional groups in the structure of the compound, and proton signals with characteristic chemical shifts for the corresponding functional groups were detected in 1H NMR spectra. In the PASS Professional 2007 program, the most probable types of biological activity of the test compound were predicted. The most significant types of biological activity are in relation to urological diseases, antiseborrheic effect, stimulator of renal function, stimulator of leukopoiesis.

Synthesis of 1,1'-oxalyldibenzotriazole, study of the kinetic and thermodynamic features of its hydrolysis and prediction of biological activity

The article describes a two-step method for the synthesis of 1,1'-oxalyl dibenzotriazole (bis(1H-benzotriazol-1-yl)ethane-1,2-dione) from benzotriazole via 1-trimethylsilylbenzotriazole, followed by reaction with oxalyl chloride; the yield of the final product is 87%. The kinetics of hydrolysis, alcoholysis and aminolysis of 1,1'-oxalyldibenzotriazole was studied in the systems acetonitrile – water (9 : 1), acetonitrile – methanol (9 : 1), acetonitrile – diethylamine (9 : 1) at 25 °C, and also by the equation Arrhenius values of the activation energy in the reactions of hydrolysis, alcoholysis, and aminolysis of 1,1'-oxalyl dibenzotriazole were calculated. To study the thermodynamic features of the reactions of obtaining this compound in the Spartan’14 1.1.4 program, a number of thermodynamic characteristics were calculated, determining the spontaneous and exothermic nature of the process. For the 1,1'-oxalyl dibenzotriazole molecule, possible conformers were found in the Molecular Operating Environment 2014.0901 software, for which the surfaces of nucleophilic susceptibility were calculated in the SCIGRESS Modeling 3.1.4 software. The structure of 1,1'-oxalyl dibenzotriazole was confirmed by IR and 1H NMR spectroscopy. The program PASS Professional 2007 predicted the most likely types of biological activity of the studied compounds. The most significant types of biological activity are in relation to renal diseases, anti-neurotoxic, anti-acid, anti-inflammatory. The obtained data allow us to choose the optimal conditions for the synthesis of 1,1’-oxalyl dibenzotriazole and to conclude that it is low stability in nucleophilic-containing media.