Synthesis of N-substituted 2,3-dichlorobicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic acid imides

Russian Journal of Organic Chemistry -     

Kinetic model of coherent synchronized ethylene monooxidation by hydrogen peroxide on a biomimetic catalyst,per-FTPhPFe<Superscript>3+</Superscript>OH/Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

A kinetic model that fits the experimental data is studied on the basis of the most probable mechanism of ethylene oxidation by hydrogen peroxide over a biomimetic catalyst, perfluorinated iron (III) tetraphenylporphyrin, deposited on aluminum oxide (per-FTPhPFe³⁺OH/Al₂O₃). Effective rate constants for the catalase and oxygenase reactions and their effective activation energies are found.     

Synthesis of bicyclo[2.2.1]hept-5-enyl methyl esters of haloacetic acids

Synthesis of norbornenyl methyl esters of a number of haloacetic acids via [4+2] cycloaddition of cyclopentadiene to allyl esters of these acids was examined. The yield and isomer composition of the synthesized compounds were examined in relation to the reaction conditions, and the best conditions for their preparation were found.     

The monooxidation of ethylene with hydrogen peroxide on the per-FTPhPFe<Superscript>3+</Superscript>OH/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> biomimetic

The gas-phase monooxidation of ethylene by hydrogen peroxide on a biomimetic heterogeneous catalyst (per-FTPhPFe³⁺OH/Al₂O₃) was studied under comparatively mild conditions. The biomimetic oxidation of ethylene with hydrogen peroxide was shown to be coherently synchronized with the decomposition of H₂O₂. Depending on reaction medium conditions, one of two desired products was formed, either ethanol or acetaldehyde. The kinetics and probable mechanism of ethylene transformation were studied.     

Synthesis of 1,4,5,6-tetrachloro-7,7-dimethoxybicyclo[2.2.1]hepta-2,5-dienylmethyl esters of p-substituted benzoic acids

The possibility of preparing 1,4,5,6-tetrachloro-7,7-dimethoxybicyclo[2.2.1]hepta-2,5-dienyl-methyl esters of p-substituted benzoic acids by [4+2]cycloaddition of tetrachlorodimethoxycyclo-pentadine to propargyl esters of the corresponding acids was examined. The optimal synthesis conditions were found. The structure of the compounds synthesized was confirmed by independent synthesis and by IR and ¹H NMR spectroscopy.     

Difference Schrödinger equation andq-oscillator model

A simple difference generalization of the one-dimensional Schrödinger equation is considered. As an application of this equation, a model of aq-harmonic oscillator with wave functions expressed in terms ofq ^–1-Hermite polynomials is constructed. Some properties of theq-Hermite—Szegö polynomials are studied.Institute of Physics, Azerbaidzhan. Translated from Teoreticheskaya i Matematicheskaya Fizika, Vol. 102, No. 2, pp. 247–257, February, 1995.     

Reaction of zirconium(IV) with 2,3,4-trihydroxiphenylazo-5′-sulfonaphthalene in the presence of diantipyrilmethane and its homologues

The effect of diantipyrilmethane and its homologues on the complexation of zirconium(IV) with 2,3,4-trihydroxiphenylazo-5′-sulfonaphthalene is studied, and conditions for the formation of mixed-ligand complexes are determined. Correlations between the acidity constants of diantipyrilmethane and its homologues and the stability constants and the specific conductivity of complexes, and degree of contrast, and the change in the Gibbs free energy are found for the complexation reaction. A method is developed for the selective photometric determination of zirconium in pyrite containing modified quartz diorite.     

PHOTOHEMOLYSIS SENSITIZED BY PSORALEN: RECIPROCITY LAW IS NOT FULFILLED

The effect of the intensity of ultraviolet-A (UV-A) radiation (366 nm) on delayed photohemolysis sensitized by psoralen (PUV-A hemolysis) was studied. It was shown that PUV-A hemolysis induced by UV-A radiation at low fluence rate (20 W m-2) develops according to the well-known colloid-osmotic mechanism: there was no threshold dose of PUV-A treatment. After irradiation all the cells were hemolysed. The rate of PUV-A hemolysis was proportional to the square of the fluence. Hemolysis was delayed in the presence of sucrose. When the fluence rate of UV-A radiation was increased to 150 W m-2, the character of PUV-A hemolysis changed drastically. A threshold fluence appeared, below which PUV-A hemolysis was not induced. At fluences slightly exceeding the threshold, only part of the cells in the suspension were lysed. The dependence of the portion of hemolysing cells on fluence was S-shaped. Increasing the fluence resulted in complete (100%) hemolysis. The rate of complete hemolysis decreased at higher fluences, but was many-fold higher than the rate of low-intensity PUV-A hemolysis at equal fluences. The main features of high intensity PUV-A hemolysis (dependences on fluence and temperature, effect of sucrose) were the same for the hemolysis induced by the addition of previously photooxidized psoralen. We suggest that high intensity PUV-A hemolysis is induced with participation of photooxidized psoralen as an intermediate.