Hetrocyclic Thiones and Their Analogs in Reactions of 1,3-Dipolar Addition: VI. Reactions of Thiazoline-2-thione with Nitrile Imines

Reactions of thiazoline-2-thione with C,N-disubstituted nitrile imines were investigated. The reaction products are substituted 2-(1,3,4-thiadiazol-2-ylideneamino)ethanethiols and bis[2-(1,3,4-thiadiazol-2-ylideneamino)ethyl] disulfides. The reaction of thiazoline-2-thione with a double excess of nitrile imine did not considerably change the process route. The structure of compounds obtained was proved by X-ray diffraction analysis. A presumable scheme is given describing the formation of compounds obtained.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 5, 2005, pp. 776–782.Original Russian Text Copyright © 2005 by Firsova, Dolgushina, Polukeev, Ioannisyan, Zavodnik, Stash, Bel’skii, Galishev.     

Reactions of 4-(o-carboranyl)pyrylium salts with nucleophilic agents. Synthesis of nitrogen heterocycles with an o-carboranyl substituent

Nitrogen heterocycles, viz., pyridines, pyridinium salts, diazepine, and pyrazoles, with an o-carboranyl substituent were obtained by reaction of 4-(o-carboranyl)-pyrylium perchlorates with nitrogen-containig nucleophilic agents, viz., ammonia, primary amines, hydrazine, and phenylhydrazine. Opening of the pyrylium ring without involvement of the carborane ring occurs under the influence of bases.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 454–458, April, 1981.     

Zur Kenntnis von Natrium-hexafluoromanganat(III)

Sodium hexafluoromanganate(III) has been synthesized by heating equimolecular quantities of Na₂MnF₅ and NaF in argon atmosphere. The compound is monoclinic witha=5.56 (1) Å,b=5.84 (1) Å,c=8.10 (2) Å, =90.7 (2) andZ=2. It is a high spin complex with _eff and the deformation of the octahedra is evident from its IR-spectra. Two enantiotropic transitions (at 562 and 653°C) and the melting point at 800°C have been observed.

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8. Mitt.: Mh. Chem.106, 483 (1975).     

Low temperature magnetic susceptibility and exchange interaction in Cs3Cr2Cl9

Magnetic susceptibility of Cs₃Cr₂Cl₉ as a single crystal is studied in the temperature range 4.2–77 K. A maximum is obtained at 25 ± 1 K. These experimental data are interpreted by considering the isotropic exchange interaction between two spin quadruplets. The exchange constant J is found to be equal to - 13 cm^?1.     

Structural and magnetic characterization of Mn3IrGe and Mn3Ir(Si1−xGex): experiments and theory

The structural and magnetic properties of a new ternary Ir-Mn-Ge phase, Mn₃IrGe, as well as the solid solution Mn₃Ir(Si_1−xGe_x), 0?x?1, have been investigated by means of X-ray and neutron powder diffraction, magnetization measurements and first principles calculations. The crystal structure is cubic, of the AlAu₄-type (an ordered form of the β-Mn structure), Z=4, space group P2₁3, and the unit-cell dimension varies linearly with the silicon content. For all compositions, antiferromagnetic ordering is found below a critical temperature of about 225 K. The magnetic structure is noncollinear, as a result of frustrated magnetic interactions on a triangular network of Mn atoms, on which the moments rotate 120° around the triangle axes. The magnitude of the magnetic moment at 10 K is 3.39(4) μ_B for Mn₃IrGe. The theoretical calculations reproduce with very good accuracy the magnitudes as well as the directions of the experimentally observed magnetic moments.     

Geminal systems. 50. Solvolysis of 1-tosyloxy-Δ2-1,2,3-triazoline-5,5-dicarboxylate esters and the structure of the solvolysis product,O-tosyl-N-α,α-bis(ethoxycarbonyl)-β-methoxyethylhydroxylamine

Solvolysis of 1-tosyloxy-²-1,2,3-triazoline-5,5-dicarboxylic acid esters (1) occurs via elimination of N₂ and leads predominantly to N--hydroxylethyl-O-tosylhydroxylamines (II), whose structure was determined unequivocally by x-ray structural analysis. The mechanism of solvolysis of triazolines (I) is discussed, along with the structural characteristics and stabilization factors of the O-tosylhydroxylamine products (II).For previous communication, see [1].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1820–1827, August, 1990.     

Formation of peroxide compounds on the oxidation of lignin by oxygen in an organic solvent

The results are given of a determination of the steady-state concentrations of peroxide compounds on the oxidation of lignin by oxygen in dioxane. An iodometric method of determining peroxides was used, with spectrophotometric control of the amount of iodine formed. It was established that the achievable steady-state concentration of peroxide compounds on the oxidation of lignin is 0.28–0.44 wt. % of O_act (oxygen pressure 1 atm, temperature 50–80°C). With a rise in the temperature, the steady-state concentration of peroxide compounds decreased. The addition of water (30 vol. %) to the organic solvent led to an increase in the rate of accumulation of peroxide compounds. It has been shown that the presence of alkaline and acidic catalysts exerts no appreciable influence on the achievable steady-state concentration and the rate of accumulation of peroxide compounds during the oxidation of lignin.Bratsk Industrial Institute. All-Union Scientific Production Combine of the Pulp and Paper Industry, Leningrad. Translated from Khimiya Prirodnykh Soedinenii, Nos. 3,4, pp. 413–417, May–August, 1992.     

Imidazoline ring cleavage in 1,3,6,10-tetraazatetracyclo-[7.3.1.02,7.06,13]trideca-4, 11-dienes,leading to the formation of diquinoxalino[1,2-a∶2′,3′-d]pyrrole derivatives

Dibenzo[d,k]-1,3,6,10-tetraazatetracyclo[7.3.1.0^2,7.0^6,13]trideca-4,11-dienes undergo addition reactions at the C₍₂₎ carbon atom with alcohols and thiols, accompanied by cleavage of the C-N bond of the imidazoline ring, to generate diquinoxalino[1,2-a2,3-d]pyrrole derivatives.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 513–522, April, 1987.     

A polymer thin-film technique to study the micromorphology of core/shell latexes

A series of poly(styrene)/poly(styrene-co-acrylonitrile) core-shell latexes were synthesized by seeded emulsion polymerization. The dried latex was dissolved in toluene and then cast on the surface of water to form a very thin film (60–90 nm). Phase separation in the thin film was studied by transmission electron microscopy (TEM). Electron micrographs of these thin films yielded fine structure and interesting morphology that was unattainable by ultramicrotoming of the corresponding compression-molded specimens. Glass transition temperatures and percent grafted polystyrene were correlated with the TEM results. As grafting increases, mixing of the two phases improves, with the resulting T_g value being between the two T_g's of poly(styrene) and poly(styrene-co-acrylonitrile).