Mechanism of the thio-claisen rearrangement of 3-methylallyl phenyl sulfide

The thio-Claisen rearrangement of isomeric 3- and 1-methylallyl phenyl sulfides was investigated. It is demonstrated that the thio-Claisen rearrangement of the 3-methyl isomer is preceded by its thioallyl rearrangement to the 1-methyl isomer. The latter undergoes thio-Claisen rearrangement to o-(3-methylallyl)thiophenol, which is cyclized to 2-ethyl-2,3-dihydrobenzothiophene and 2-methylthiochroman under the reaction conditions.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1191–1194, September, 1981.     

Synthesis of Pyrazolines Based on Levoglucosenone

The 1,3-dipolar cycloaddition of diazomethane to levoglucosenone was found to occur regio- and stereoselectively to form optically active 9,11-dioxa-4,5-diazatricyclo[6.2.1.0^2,6]undec-4-en-7-one. Levoglucosenone was found to react with methyldiazoacetate to give the 2:1 adduct.     

Condensation of aryl bromides with styrenes,catalyzed by nickel complexes in the presence of zinc

Conclusions Condensation of aryl bromides with styrenes in acetonitrile in the presence of nickel organometallic complex catalysts and metallic zinc occurs regio- and stereoselectively to give E-stilbenes.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2508–2511, November, 1987.     

α-Aminoazoles in the Synthesis of Heterocycles. Intermediates of Reaction between 3(5)-Aminopyrazoles and Trifluoroacetylacetone

Russian Journal of Organic Chemistry -     

Formation of Negative Hydrogen Ions in a Ne–H2 Hollow Cathode Discharge

The formation of negative hydrogen ions in a conventional hollow cathode discharge has been investigated. A mixture of Ne and H₂ proved to be more advantageous compared to pure hydrogen. The study has been performed by solving the electron Boltzmann equation, coupled with a system of balance equations for neon and hydrogen neutral and charged particles. The vibrational distribution function of hydrogen has been calculated. Our calculations show unusually high population of vibrationally excited hydrogen molecules in a Ne–H₂ mixture, which explains the high density of negative hydrogen ions under optimal conditions (total gas pressure of few Torr, hydrogen number mole fraction of 1–10% and discharge current of 10–100 mA). Line intensities originating from highly excited neon states vs. hydrogen pressure have been calculated and a comparison with existing experimental results has been made.     

Nitroazines. 4. Polarographic behavior of 5-nitropyrazolo[3,4-b]pyridines and the esr spectra of their electrochemically generated free radicals

1-Methyl- and 1-phenyl-substituted derivatives of 5-nitropyrazolo[3,4-b]pyridines are reduced at a dropping mercury electrode in a single one-electron wave with the formation of radical anions in interval of potentials from –0.94 to –1.06 V. Compounds unsubstituted at the N(₁) nitrogen atom give an additional polarographic wave at E_1/2 = –1.4 V due to the reduction of the deprotonated form (anion). The potentials and HFS constants of the ESR spectra of the corresponding electrochemically generated free radicals are given.For Communication 3, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 689–693, May, 1985.     

Matrix polyelectrolyte microcapsules: new system for macromolecule encapsulation

A new approach to fabricate polyelectrolyte microcapsules is based on exploiting porous inorganic microparticles of calcium carbonate. Porous CaCO3 microparticles (4.5-5.0 microns) were synthesized and characterized by scanning electron microscopy and the Brunauer-Emmett-Teller method of nitrogen adsorption/desorption to get a surface area of 8.8 m2/g and an average pore size of 35 nm. These particles were used as templates for polyelectrolyte layer-by-layer assembly of two oppositely charged polyelectrolytes, poly(styrene sulfonate) and poly(allylamine hydrochloride). Calcium carbonate core dissolution resulted in formation ofpolyelectrolyte microcapsules with an internal matrix consisting of a polyelectrolyte complex. Microcapsules with an internal matrix were analyzed by confocal Raman spectroscopy, scanning electron microscopy, force microscopy, and confocal laser-scanning fluorescence microscopy. The structure was found to be dependent on a number of polyelectrolyte adsorption treatments. Capsules have a very high loading capacity for macromolecules, which can be incorporated into the capsules by capturing them from the surrounding medium into the capsules. In this paper, we investigated the loading by dextran and bovine serum albumin as macromolecules. The amount of entrapped macromolecules was determined by two independent methods and found to be up to 15 pg per microcapsule.     

Quantitative analysis of undefined mixtures - "fishing net" algorithm

An approach for quantitative analysis of mixtures with unknown individual responses of the components is discussed. Although it is based on a resolution of overlapping bands technique, the main emphasis is not given to the computational facets of curve fitting. A logical procedure is described, allowing estimation of the unknown concentrations in the mixture, and both the number of overlapping bands and their assignment to the components in the solution to be determined automatically. A general conclusion about the precision of the method cannot be defined, because it depends on the extent of overlapping of the individual spectra of the components and their complexity. Using this procedure a complicated three-component acid-base equilibrium of a halochromic dye in solution is studied.