V. R. Flid

Unconventional catalytic allylation of 5-norbornene-2,3-dicarboxylic anhydrides : 7-oxa and 7-aza analogues

The catalytic allylation of 7-oxanorbornene, 7-azanorbornene, and bicyclo[2.2.2]octenoic anhydride was performed for the first time. It was found that the structures of allylation products and ratios between them were analogous to those for corresponding carbocyclic derivatives. The presence of a substituent at the double bond of a substrate makes this reaction impossible. Comparative experiments were performed for evaluating the relative reactivity of double bonds in 7-oxanorbornene, 7-azanorbornene, and their carbocyclic analogs.

Regularities of glycidol synthesis by the liquid-phase epoxidation of allyl alcohol with hydrogen peroxide

The main features of the liquid-phase epoxidation of allyl alcohol by hydrogen peroxide in an organic solvent in the presence of the titanium-containing zeolite in the batch reactor were studied. The influence of the amount of the solvent, ratio of reactants, and temperature on the rate of glycidol synthesis was revealed.

Quantum chemical study of the mechanism of catalytic [2+2+2] cycloaddition of acrylic acid esters to norbornadiene in the presence of nickel(0) complexes

The mechanism of the [2+2+2] cycloaddition of ethyl acrylate to norbornadiene (NBD) catalyzed by Ni0 complexes was modeled in terms of the density functional theory (DFT) at the PBE level. The formation of the first C—C bond between the coordinated NBD and ethyl acrylate molecules is the rate-determining step of the process. The low stereoselectivity of the reaction is due to the close matching of the activation barriers for the formation of exo- and endo-cycloadducts (25.6 and 24.9 kcal mol−1, respectively).

A Kinetic Model for the Epoxidation of Allyl Alcohol with Hydrogen Peroxide on Titanium Silicate TS-1

The kinetic regularities of the oxidation of allyl alcohol into glycidol in the presence of titanium silicate are studied at varied initial concentrations of the reagents, products, and temperature. The probable mechanism is used as the basis to develop a substantial kinetic model, which adequately describes the obtained experimental data.

The study of epoxidation of allyl chloride in methanol in the presence of extruded titanium containing silicalite

The liquid-phase epoxidation of allyl chloride in methanol with aqueous solution of hydrogen peroxide was conducted in the presence of extruded titanium containing silicalite and the physico-chemical features of the process were investigated. The effect of the amount of solvent, the initial ratio of the allyl chloride to hydrogen peroxide and the temperature of the process on the yield of the target product (epichlorohydrin) and by-products (3-chloro-1,2-propanediol and 3-chloro-1-methoxypropanol-2) was studied. Based on the obtained results, the optimum conditions of synthesis of epichlorohydrin for a laboratory scale continuous setup were recommended.

Study of alkene epoxidation in the presence of extruded silicalite titanium

Main features of liquid-phase epoxidation of propylene, allyl chloride, and allyl alcohol by aqueous solution of hydrogen peroxide in the presence of extruded titanium silicalite in methanol medium have been investigated. The effects of the solvent, the initial ratio of the organic substrate: hydrogen peroxide, and temperature on the yield of main products and by-products were elucidated. Based on the obtained features the conditions for the synthesis of propylene oxide, epichlorohydrin, and glycidol in a laboratory continuous set-up were established.

Kinetics of propylene epoxidation with hydrogen peroxide catalyzed by extruded titanium silicalite in methanol

The kinetics of propylene oxidation into propylene oxide in the presence of extruded titanium silicalite was studied. Based on the experimental data, a kinetic model of the process was designed and the activation energies of the target and side reactions, the rate constants, and the adsorption equilibrium constants were determined. The adequacy of the proposed kinetic model was verified on a continuously-operated test bench laboratory unit.

Catalytic syntheses of polycyclic compounds based on norbornadiene in the presence of nickel complexes: VI. Heterogenized catalyst for isomerization reactions of norbornene derivatives

The kinetics and mechanism of the thermal izomerization of 5-exo-methyl-tricyclo[3.2.1.05,7]octene-2 into 2-methyl-tetracyclo[3.2.1.02,7.04,6]octane are reported. The use of catalysts based on nickel compounds is demonstrated. As compared to the other catalytic systems, the heterogenized nickel catalyst obtained by thermal treatment of nickel norbornadiene complexes shows much better performance characteristics (selectivity, specific activity, and service life).

Catalytic syntheses of polycyclic compounds based on norbornadiene in the presence of nickel complexes: V. Codimerization of norbornadiene and methyl vinyl ketone on heterogenized nickel catalysts

A new heterogenized nickel catalyst was developed for the codimerization of norbornadiene and methyl vinyl ketone. This catalyst considerably improved the performance characteristics of the process (selectivity, specific activity, and operating time), as compared with available analogs. A thermogravimetric study of the formation of the active component of the catalyst was performed. Factors affecting the selectivity and productivity of the process were determined.