Selective synthesis of di(propen-1-yl)sulfone and di(propen-1-yl)sulfoxide

Convenient selective methods of synthesis of the title compounds, based on oxidation of di(propen-1-yl)sulfide with 30% H₂O₂, have been developed.Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, 664033 Irkutsk. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 675–679, March, 1992.     

稀土铜硫化合物TbCuS2的合成和晶体结构

Terbium copper disulfide, TbCuS₂, has been synthesized in the reaction of the elements in a KI flux at 850 ℃. The compound crystallizes in space group P2₁/c of the monoclinic system with four formula units in a cell of dimensions of a= 0.639 3(1) nm, b=0.702 5(1) nm, c=0.670 8(1) nm, β=98.097(4)°, and V=0.298 3(1) nm³ at 153 K. The structure comprises two-dimensional ²_∞[CuS₂] layers along [100] separated by the Tb atoms. In the structure, each Tb and Cu atoms are coordinated to seven and four S atoms, respectively. CSD: 415490.     

沉淀溶解法制备纳米硫化锌

以烷基黄原酸锌和硫化钠分别为锌源和硫源，采用烷基黄原酸锌沉淀溶解法制备了粒度可调、粒径分布比较窄的面心硫化锌纳米粒子，利用比表面积(BET)测定、透射电镜(TEM)、粉末X射线衍射(XRD)、傅里叶转换红外光谱(FTIR)等方法对合成的硫化锌纳米粒子进行了表征。结果表明随着烷基黄原酸锌链长的增长，通过添加硫化钠而生成的硫化锌纳米粒子的粒径逐渐减小。本文还对沉淀溶解法制备纳米硫化锌的溶液化学反应机理进行了探讨。     

Reaction of magnesium alkylidene carbenoids with lithium acetylides and lithium thiolates: a novel synthesis of conjugated enynes and vinyl sulfides

Magnesium alkylidene carbenoids were generated from 1-chlorovinyl p-tolyl sulfoxides with i-PrMgCl at −78 °C in THF or toluene via the sulfoxide-magnesium exchange reaction. Reaction of the generated magnesium alkylidene carbenoids with lithium acetylides or lithium thiolates gave conjugated enynes or vinyl sulfides, respectively, in moderate to good yields. The intermediate of this reaction was found to be the alkenyl anion and it could be trapped with some electrophiles to give tetra-substituted conjugated enynes and vinyl sulfides.     

Gas chromatographic analysis of traces of hydrogen sulfide in hydrogen

Summary A simple gas chromatographic method has been developed for analysis of hydrogen sulfide in hydrogen at the 0.5 to 100 ppm level. After enriching the traces of hydrogen sulfide by absorption in a gas loop packed with the chosen column support at 77 K it was determined by using a Chromosorb G column with silicone 550 and phthalic anhydride as liquid phases, hydrogen as carrier gas and a thermal conductivity detector. The detection limit was found to be about 0.5 ppm of hydrogen sulfide.     

Reactions of hexamethylditin and trimethyltin sulfide withN-thio-derivatives of phthalimide

The initial formation of organotin derivatives with Sn-S-N bonds in heterolytic reactions of hexamethylditin or trimethyltin sulfide withN-(chlorothio)phthalimide is suggested. Subsequent interaction of these compounds with sulfenyl chloride affordsN, N-thioorN, N-dithiobisphthalimide. Homolytic reaction of hexamethylditin withN, N-dithiobisphthalimide also occursvia an organotin intermediate, which, in the absence of a nucleophilic reagent, eliminates sulfur and converts intoN-trimethylstannylphthalimide.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2111–2114, December, 1993.     

Synthesis, crystal structure and properties of K2Ta2S10: A novel ternary tantalum polysulfide with TaS8 polyhedra forming infinite anionic chains

The new ternary alkali tantalum polysulfide K₂Ta₂S₁₀ has been synthesized by reacting TaS₂ with an in situ formed melt of K₂S₃ and S at 773 K. The compound crystallizes with four formula units in the monoclinic space group P2₁/n (No. 14) with lattice parameters of . The structure contains two different zigzag chain anions [TaS₅]⁻, running parallel to the crystallographic b-axis separated by potassium cations. The two crystallographically independent tantalum atoms are in a distorted bi-capped trigonal prismatic environment of eight sulfur atoms which was never observed before. The TaS₈ polyhedra share three S atoms on each side to form the anionic chains. The compound was characterized with FIR and Raman spectroscopy.     

Synthesis of thiadiazabicyclane and bis-1,3,5-dithiazinane by cyclothiomethylation of aliphatic diamines with CH2O and H2S

Cyclocondensation of aliphatic diamines with CH₂O and H₂S (1:3:2 ratio, 0 °C) was carried out to give thiadiazabicyclanes and dithiadiazabicyclanes (1:6:4 ratio), which were previously difficult to synthesize. Symmetric α,ω-bis-1,3,5-dithiazinanes were synthesized at 80 °C by this reaction. The stereochemistry of thiadiazabicyclanes was assigned by ¹H and ¹³C NMR spectroscopy and by theoretical DFT calculations, and of bis-dithiazinanes by X-ray diffraction study in the solid state.     

Sulfide Gels and Films: Products of Non-Oxide Gelation

The preparation of concentrated sols and transparent stiff gels of II-VI semiconductors nanocrystals is reported. A two-step process for the production of cadmium sulfide is reported. Sol stabilization and gelation control are achieved through successive passivation and depassivation of the surface of the nanocrystals which are complexed with thiols. The mechanisms driving the aggregation and the gelation are explained on the basis of NMR and SAXS experiments. Thin films as well as monoliths can be produced. The general principles of the method presented are not restricted to chalcogenide systems and thus enlarge the domain of application of the inorganic sol-gel process.     

Indirect Determination of Sulfide by Cold Vapor Atomic Absorption Spectrometry

A method for the determination of sulfide based on its interference with the determination of Hg by cold vapor atomic absorption spectrometry is described. The decrease in mercury absorbance at 253.7nm is proportional to the concentration of sulfide over the range of 10–320ngmL^–1. The limit of detection was found to be 7ngmL^–1 and the relative standard deviation (R.S.D.) for the determination of different concentrations of sulfide was in the range of 1.8–2.2%. This method was applied to the determination of sulfide in whole human blood after gas-phase separation.