Electronic regioselectivity in the reactions of pyridinium ylides with tetracyanoethylene

Highly regioselective reactions of pyridinium ylides with tetracyanoethylene occur via an Ad_N-E mechanism to form Z-isomers of 3-aroyl-3-(1-pyridinio)-1,1,2-tricyano-2-propenides-1, corresponding in structure to 1,4-ylides with maximum charge separation. If the unsaturated nitrite starting material contains a nucleofugal group 1,2-elimination predominates over 1,3-elimination.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1087–1094, August, 1991.     

Synthesis of substituted 3-thiophenecarbaldoximes containing unsaturated groups at C2

A convenient preparative method was developed to obtain substituted 2-allylthio-5- methyl-3-thiophenecarbaldoximes, which are starting compounds in the synthesis of fused heterocycles containing the thiophene ring, by the successive action of sodium in liquid ammonia and substituted -halopropenes on 2-methylthio-5-methyl-3-thiophenecarbaldoxime.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, PP. 247–251, January, 1991.     

Pyrrolo[2,1-b]benzothiazole derivatives

A new method for obtaining pyrrolobenzothiazole derivatives, which can be used for the specific synthesis of polymethine dyes with predesignated properties, was developed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 549–553, April, 1991.     

Molecular structure of N-mesityl-6H-anthra[9,1-bc]pyrrol-6-one

The molecular and crystalline structure of 1-(2,4,6-trimethylphenyl)-6H-anthra-[9,1-bc]pyrrol-6-one was determined by the x-ray structural method. There is a larger uniformity of the bonds in the benzene ring of the isoindole fragment than in the N-substituted isoindoles; this derives from the electronic influence of the keto group. The structure of the whole molecule does not have marked 1,10-anthraquinoid character.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 485–490, April, 1988.     

Laboratory and Industrial Applications of Microwave Techniques

The use of microwave techniques in scientific research is reviewed. Also some semicommercial-scale microwave units are examined.     

High-Sensitivity Determination of Hydrocarbon Impurities in Arsine by Reaction Gas Chromatography

It is shown that the results of determining methane in high-purity arsine by reaction gas chromatography can be overestimated by more than two orders of magnitude. This overestimation is caused by the formation of methane as a side product of the reaction. Cryogenic preconcentration at the injection stage is proposed to improve the accuracy of determination of methane, and the cryofocusing of impurity hydrocarbons is proposed to improve separation. Detection limits of (3–10) × 10^–6 vol % are achieved for C₁–C₅ hydrocarbons.     

Effect of Mechanochemical Activation on the Catalytic Properties of Ferrites with the Spinel Structure

It was found experimentally that stacking defects formed in the mechanochemical activation of zinc ferrite enhanced the specific catalytic activity in the reaction of CO oxidation. The specific rate of CO oxidation was a linear function of defect concentration, which was determined using Mössbauer spectroscopy and X-ray diffraction. A conclusion was drawn that the same centers are responsible for an increase in the catalytic activity, the sorption capacity for hydrogen sulfide, and the reactivity of zinc ferrite in the interaction with hydrochloric acid. It was assumed that analogous factors caused an increase in the catalytic activity and reactivity of magnesium ferrite.     

Synthesis of Aryl Ethers by Nonactivated Aromatic Nucleophilic Substitution Reactions

The results of a kinetic study of model reactions between substituted phenols and bromobenzene in the presence of potassium carbonate and the copper(I) chloride–8-hydroxyquinoline catalytic complex in N,N-dimethylformamide are presented. The reactions were found to obey a first-order rate law. Both orbital and charge interactions should be taken into account in a consideration of the effect of the structural characteristics of reactants on the rate of reaction. The kinetics of substitution of the phenoxide anion for an aromatically bound halogen atom in activated and nonactivated systems with the formation of practically valuable aryl ethers were comparatively studied. The results presented provide an opportunity to distinguish the common features and regularities of activated and nonactivated aromatic substitution in the test systems.