V. M. Zelikman

Catalysts based on the immobilized complexes of copper with quaternary ammonium bases for chlorination of alkanes with carbon tetrachloride

The complexes of copper chloride with quaternary ammonium bases supported on silica are highly active in the reaction of carbon tetrachloride with decane was found in the presence of an electron donor (ethanol). The effectiveness of the catalysts depends on the method of their deposition onto the support. The catalysts obtained as a result of covalent binding with the surface through the formation of siloxane bonds (immobilization) exhibit high stability and higher activity than the analogues prepared by the impregnation of the support with the catalytic complex. The introduction of ethanol into the reaction system substantially increases the activity and stability of all of the catalysts.

Carbon Tetrabromide-A New Brominating Agent for Alkanes and Arylalkanes

Quantitative catalytic bromination of alkanes, cycloalkanes, and arylalkanes with carbon tetrabromide as brominating agent was accomplished for the first time.

QUATERNARY AMMONIUM POLYCHLORIDES AS EFFICIENT REAGENTS FOR CHLORINATION OF UNSATURATED COMPOUNDS

Chlorination of unsaturated compounds by benzyltributylammonium polychlorides results in higher yields of addition products compared to those obtained with molecular chlorine.

Immobilized copper- and molybdenum-containing ionic liquids in oxidation of sulfides

The synthesis and comparative analysis of catalytic properties of Cu- and Mo-containing ethylpropylimidazolium derivatives immobilized on silica-series mineral supports have been performed. The oxidation of diethyl sulfide and methyl phenyl sulfide with oxygen and hydrogen peroxide in a hydrocarbon medium has been studied as a model process. The catalyst based on ethylpropylimidazolium polymolybdates is the most active and stable in the oxidation of methyl phenyl sulfide.

Reactions of polyhalomethanes with olefins catalyzed by copper complexes with aromatic amino alcohols

Copper complexes with amino alcohols structurally similar to ephedrin (1-phenyl-3-(N-methylamino)propan-1-ol and 1-phenyl-2-(N-methylamino)ethanol) are catalytically very active in the free-radical addition of CCl4 and CBr4 to linear alk-1-enes. These amino alcohols themselves are initiators of radical addition reactions, and, in the reaction with CBr4, they are more active than the metal complexes. In the presence of the amino alcohols, as distinct from classical radical initiators, the reaction is highly selective and affords an addition product. An analysis of kinetic equations and the data obtained for the reaction involving CHCl3 suggest that the amino alcohols and the corresponding metal complexes are involved in different ways in the addition of CCl4 and CBr4 to linear alk-1-enes.

Immobilized ionic liquids based on molybdenum- and tungsten-containing heteropoly acids: Structure and catalytic properties in thiophene oxidation

Comparative analysis of heterogeneous catalysts for the peroxide oxidation of thiophene is conducted. The catalysts are imidazole ionic liquids (ILs) containing anions of phosphomolybdic and phosphotungstic acids immobilized on mineral supports. Immobilization is implemented by the covalent bonding of an IL fragment to a silica surface or by adsorption on alumina. The catalysts are active not only in the model oxidation of thiophene in isooctane, but also in the desulfurization of a straight-run diesel fraction and the “synthetic crude oil” derived from oil shale.

Effect of the composition of the immobilized copper-containing ionic liquid on the dodecyl mercaptan oxidation kinetics

Basic kinetic parameters of the catalytic oxidation of dodecyl mercaptan in kerosene in the presence of silica-immobilized pyridinium or imidazolium chlorocuprate complexes have been determined. The composition of the copper-containing anions and the oxidation kinetics depend on the nature of the ionic liquid and on the method of its synthesis. The compositions developed in this study are usable in the removal of hydrogen sulfide and light mercaptans from the oil stripping gas.