New method for the synthesis of β-bromostyrenes

A new stereoselective method was developed for the synthesis of -bromostyrenes (E/Z > 5/1) starting from hydrazones of aromatic aldehydes and bromoform in the presence of CuCl.     

Reactions of 1-aryl-2-bromodiazene 1-oxides with acids and bases

The reactions of 1-aryl-2-bromodiazene 1-oxides with HCl in nonaqueous media give aryldiazonium chlorides, while 1,3,3-substituted triazenes-1 are formed in the reactions with secondary amines. Using 2-{¹⁵N} label, it was shown that the aryl group does not migrate in these reactions. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 613–615, March, 1997.     

The Monohydrate of Basic Mercuric Nitrate, [Hg(OH)](NO3)(H2O)

Colourless single crystals of [Hg(OH)](NO₃)(H₂O) were obtained by slow evaporation of an aqueous solution of Hg(NO₃)₂ and Bi(NO₃)₃. The crystal structure (orthorhombic, Pbca, Z = 8, a = 943.2(2), b = 697.6(1), c = 1349.0(2) pm, R₁(all) = 0.0780) contains [Hg(OH)] = …OH–Hg–OH–Hg… zig zag chains (O–Hg–O angle: 168°, Hg–O–Hg angle: 112°, Hg–OH distance: 212 pm) to which one water molecule is attached loosely. The [Hg(OH)](H₂O) chains are connected via bis‐monodentate‐bridging nitrate ions to corrugated layers that are stacked in the [001] direction. Hg²⁺ has an effective 2+2+2(+1) coordination.     

Thermodynamic characteristics of solvation of individual ions in ethanol at −50 to 55°C

Experimentally determined are the enthalpies of solution of 12 electrolytes (LiBr, LiI, NaBr, NaI, NaBPh₄, Et₄NCl, Et₄NBr, Pr₄Br, Bu₄NBr, Am₄NBr, Ph₄PCl, Ph₄PBr) in ethanol at –50 to 55°C. _sH^o values obtained on the basis of four different extrapolation equations are analyzed. The effect of temperature changes on the thermodynamic parameters of solvation indindividual ions are calculated using thermodynamic data for the salt crystals (lattice) with the assumption that _solvC _p ^o (Ph₄P⁺)=_solvC _p ^o (Ph₄P^-).     

Thermal Analysis of Cobalt(II) Salts with some Carboxylic Acids

The thermal analysis of CoC₂O₄·2H₂O, Co(HCOO)₂·2H₂O and Co(CH₃COO)₂·4H₂O was carried out with simultaneous TG-DTG-DTA measurements under non-isothermal conditions in air and argon atmospheres. The intermediates and the end products of decomposition were characterised by X-ray diffraction and IR and UV-VIS spectroscopy. The decomposition of the studied compounds occur in several stages. The first stage of dissociation of each compound is dehydration both in air and argon. The next stages differ in air and argon. The final product of the decomposition of each compound in air is Co₃O₄. In argon it is a mixture of Co and CoO for cobalt(II) oxalate and cobalt(II) formate but CoO for cobalt(II) acetate. This revised version was published online in August 2006 with corrections to the Cover Date.     

Chemistry of <Emphasis Type="Italic">N,N</Emphasis>-bis(silyloxy)enamines 7. Quaternization of tertiary amines and nitrogen-containing heterocycles by <Emphasis Type="Italic">N,N</Emphasis>-bis(silyloxy)enamines

Coupling of N,N-bis(silyloxy)enamines with tertiary amines and nitrogen-containing heterocycles affording the corresponding functionalized ammonium or iminium salts was studied. The area of its application was determined, and optimal procedures for the synthesis of the target products were proposed. The mechanism including the formation of conjugated nitroso alkene or a silylnitrosonium cation as key intermediates is discussed.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2137–2143, October, 2004.     

金属盐对O2/CO2煤粉混燃钙基脱硫反应的影响

利用添加剂调制改性的方法，考察了以碳酸钠为代表的金属盐对石灰石微观结构的影响，得出调制改性优化了石灰石的物理结构，并在离子比γ为15∶1的加入量效果最佳。在此基础上，借助定硫仪比较了O2-CO2气氛下调制前后石灰石对燃煤SO2释放的影响，并对燃烧产物进行灰熔点分析及灰成分的XRD测试。实验结果表明，在不影响煤粉燃烧结渣特性的前提下，改性后的石灰石可以更有效地抑制SO2的排放，固硫效果在1 000 ℃时达到最佳。     

Preparation, structure and ethylene polymerization behavior of mixed-halide nickel(II) complexes and cobalt(II) complex containing imidazolium

Preparation of two imidazolium salts, two monomeric nickel(II) and one cobalt(II) complexes bearing imidazolium ligands is described, The solid-state structures of these compounds have determined by single-crystal X-ray diffraction. After activation with methylaluminoxane (MAO) the nickel complexes show moderate catalytic activities of up to 6 × 10⁵ g PE mol⁻¹Ni h⁻¹ for polymerization of ethylene. Catalytic activities, molecular weights have been investigated under the various reaction conditions.     

Oxidative coupling of malononitrile with formation of 1,1,2,3,3-pentacyanopropene salts

A simple and convenient route for the synthesis of 1,1,2,3,3-pentacyanopropene salts is reported. These salts are formed by interaction of malononitrile with SeO₂ in presence of organic N-containing bases or pyridinium salts.     

Unusual ion pairs and their relationship to acid ionization

Osmotic and activity coefficients, determined from isopiestic measurements, are presented for aqueous solutions of eight tetramethylguanidinium salts. It is proposed that both hydronium and tetramethylguanidinium ions are capable of forming stable ion pairs with many anions by means of bridged hydrogens forming six-membered rings and that these ion pairs are stable in rather dilute aqueous solutions.