<i>N,N</i>-bis-(dimethylfluorosilylmethyl)amides of <i>N</i>-organosulfonylproline and sarcosine: synthesis, structure, stereodynamic behaviour and <i>in silico</i> studies

(O→Si)-Chelate difluorides R3R2NCH(R1)C(O)N(CH2SiMe2F)2 (9a–c, R1R2 = (CH2)3, R3 = Ms (a), Ts (b); R1 = H, R2 = Me, R3 = Ms (c)), containing one penta- and one tetracoordinate silicon atoms were synthesized by silylmethylation of amides R3R2NCH(R1)C(O)NH2, subsequent hydrolysis of unstable intermediates R3R2NCH(R1)C(O)N(CH2SiMe2Cl)2 (7a–c) into 4-acyl-2,6-disilamorpholines R3R2NCH(R1)C(O)N(CH2SiMe2O)2 (8a–c) and the reaction of the latter compounds with BF3·Et2O. The structures of disilamorpholines 8a,c and difluoride 9a were confirmed by an X-ray diffraction study. According to the IR and NMR data, the O→Si coordination in solutions of these compounds was weaker than that in the solid state due to effective solvation of the Si–F bond. A permutational isomerisation involving an exchange of equatorial Me groups at the pentacoordinate Si atom in complexes 9a–c was detected, and its activational parameters were determined by 1H DNMR. In silico estimation of possible pharmacological effects and acute rat toxicity by PASS Online and GUSAR Online services showed a potential for their further pharmacological study

On the tree-transformation power of XSLT

XSLT is a standard rule-based programming language for expressing transformations of XML data. The language is currently in transition from version 1.0 to 2.0. In order to understand the computational consequences of this transition, we restrict XSLT to its pure tree-transformation capabilities. Under this focus, we observe that XSLT~1.0 was not yet a computationally complete tree-transformation language: every 1.0 program can be implemented in exponential time. A crucial new feature of version~2.0, however, which allows nodesets over temporary trees, yields completeness. We provide a formal operational semantics for XSLT programs, and establish confluence for this semantics

Aryl oligogermanes as ligands for transition metal complexes

The ligand properties of a series of aryl oligogermanes R3Ge‐GeAr3, 3‐7 (Me3Ge‐GePh3 (3), Me3Ge‐Ge(pTol)3 (4), Ph3Ge‐GePh3 (5), (C6F5)3Ge‐GePh3 (6), Ph3Ge‐GeMe2GePh3 (7)), for the synthesis of transition metal carbonyl complexes such as R3Ge‐GeAr2(R’C6H4‐η6)M(CO)3 (M = Cr, 3a‐7a; M = Mo, 3b; M = W, 3c) were investigated. The target complexes were obtained in moderate yields using several different synthetic approaches. The physicochemical properties of these new derivatives were investigated by IR, UV/vis, NMR spectroscopy, electrochemistry and DFT calculations. The molecular structures of 3c, 4a and 5a were studied by single crystal X‐ray diffraction analysis. A comparative analysis of donor‐ and acceptor properties of aryl oligogermanes as ligands for transition metal carbonyl complexes is reported

Mathematical model of stacked one-sided arrangement of the burners

Paper is aimed at computer simulation of the turbulent methane-air combustion in upgraded U-shaped boiler unit. To reduce the temperature in the flame and hence NOx release every burner output was reduced, but the number of the burners was increased. The subject of studying: complex of characteristics with space-time fields in the upgraded steam boiler E-370 with natural circulation. The flare structure, temperature and concentrations were determined computationally

Polymerization of the new double-charged monomer bis-1,3(N,N,N trimethylammonium dicyanamide)-2-propylmethacrylate and ionic conductivity of the novel polyelectrolytes

The achievement of high ionic conductivity in single-ion conducting polymer electrolytes is one of the important aims for various electrochemical devices including modern lithium batteries. One way to enhance the ionic conductivity in polyelectrolyte systems is to increase the quantity of charge carriers in each monomer unit. Highly charged poly(bis-1,3(N,N,N-trimethylammonium)-2-propylmethacrylate) with one of the most conducting anions, namely dicyanamide, was prepared via free radical bulk polymerization or using ionic liquids as reaction medium. The cationic polymers of the double-charged monomer have molar masses up to equation image = 1,830,000 g/mol and the ionic conductivity equal to 5.51 × 10−5 S/cm at 25°C. The film forming ability, crystallinity, thermal stability, and glass transition temperatures of the new polymeric ionic liquids obtained from detailed studies are presente

13C NMR spectrum of crystalline [Rh(Acac) (CO)2]: A contribution to the discussion on [Rh(Acac) (CO)2] molecular structure in the solid state

13C MAS NMR spectrum of polycrystalline [Rh(Acac) (CO)2] (1) displays separate signals from all 7 carbon atoms: 2 doublets from CO ligand carbons along with 5 singlets from Acac carbons. GIPAW calculation of 13C shielding tensor values also revealed non-equivalence of all carbon atoms in molecule 1 in the anisotropic medium of the crystal lattice. Apparently, the C2v symmetry of molecule 1 is broken owing to the asymmetry of its contacts to the neighboring molecules. For example, the contacts O⋯HC of two CO ligands of molecule 1 to the CH group of the closest molecule in the adjacent stack are markedly different: the distances OH are 2.72 and 4.38 Å, the distances OC are 3.65 and 5.00 Å, the angles OHC are 164.9° and 126.4°

Reaction of Picolinamides with Ketones Producing a New Type of Heterocyclic Salts with an Imidazolidin-4-One Ring

Reactions of picolinamides with 1,3-propanesultone in methanol followed by the treatment with ketones led to a series of previously unknown chemical transformations, yielding first pyridinium salts (2a–f), with a protonated endocyclic nitrogen atom, and then heterocyclic salts (3a–j) containing an imidazolidin-4-one ring. The structures of intermediate and final products were determined by IR and 1H, 13C NMR spectroscopy, and X-ray study. The effects of the ketone and alcohol structures on the product yield were studied by quantum-chemical calculations. The stability of salts 3a–j towards hydrolysis and alcoholysis makes them excellent candidates for the search for new types of biologically active compounds

Modern Trends of Organic Chemistry in Russian Universities

© 2018, Pleiades Publishing, Ltd. This review is devoted to the scientific achievements of the departments of organic chemistry in higher schools of Russia within the past decade