Diastereoselective synthesis of all eight l-hexoses from L-ascorbic acid

[reaction: see text] A novel versatile method for the synthesis of all eight diastereomerically pure L-hexoses was developed. L-Ascorbic acid was converted to two diastereomers A. These alpha-hydroxy esters were transformed into four gamma-alkoxy-alpha,beta-unsaturated esters C via the intermediates B and subsequent Wittig olefination reactions. Each one of compounds C was subjected to dihydroxylation to provide a set of two diols D. Anti/syn-differentiation in diol formation was manipulated by using (DHQD)2PHAL and (DHQ)2PHAL as chiral ligands. Further two-step reaction sequence affords all eight diastereopure L-hexoses.     

Efficient and selective multicomponent oxidative coupling of two different aliphatic primary amines into thioamides by elemental sulfur

An efficient and selective multicomponent oxidative coupling of two different aliphatic primary amines into thioamides by elemental sulfur under solvent-free conditions has been developed.     

Ethylene Polymerization over Supported Titanium-Magnesium Catalysts: Heterogeneity of Active Centers and Effect of Catalyst Composition on the Molecular Mass Distribution of Polymer

New experimental approach was used for analysis of molecular weight distribution (MWD) of polymers produced over titanium-magnesium catalysts (TMC). Polymers were fractionated on to fractions with narrow MWD (polydispersity (PD) values Mw/Mn ≤ 2). Then some of these fractions were combined to get the minimal quantity of fractions with PD values close to 2 (Flory components). It was found that three fractions corresponding to three groups of active centers are sufficient for proper fitting experimental MWD curve for PE obtained over TMC with different Ti content and with different hydrogen concentration in polymerization.     

1-Amino-2-nitraminoethane

The mol­ecule of title compound, C₂H₇N₃O₂, has a zwitterionic structure. All non-H atoms, apart from the terminal N atom of the NH₃ group, lie in the same plane, with a maximum deviation of 0.056 (1) Å for the amine N atom of the nitr­amine group, whereas the deviation of the terminal N atom of the NH₃ group from the same plane is 1.222 (2) Å. Intermolecular hydrogen bonds within the crystal form a three-dimensional network.     

Luminescence of different modifications of crystalline silicon dioxide: Stishovite and coesite

Luminescence of very small samples of single crystals of coesite and stishovite has been studied. The spectra were detected under ionizing radiation (X-ray and electron beam) and the decay kinetics of cathodoluminescence in the range of time from 10 ns to 3 ms was measured. The coesite luminescence possesses a broad band at 3 eV with exponential decay about 680 μs at 80 K. The nature of this luminescence was explained as a self-trapped exciton creation in tetrahedron framework. The stishovite luminescence possesses two bands—blue (2.8 eV) and UV (4.7 eV). The UV band intensity grows more than 20 times with irradiation dose from initial level. This shows that the corresponding luminescence centers could be induced by the radiation. The decay of the UV band possesses a fast and a slow component. The determination of the fast decay parameters is beyond the capabilities of our apparatus (less than 10 ns), whereas the slow decay of the UV is non-exponential and takes place in the range of hundreds of microsecond. The blue band decay kinetics can be well approximated by power law ∼t⁻², which may correspond to recombination of defects created by radiation. The stishovite single crystal luminescence is very similar to that of germanium dioxide single crystal of rutile structure. The nature of the stishovite luminescence is explained as recombination of defects created by irradiation in octahedron-structured lattice.     

Energy-efficient dehydrogenation of methanol in a membrane reactor: a mathematical modeling

A two-dimensional non-isothermal stationary mathematical model of the catalytic membrane reactor for the process of methanol dehydrogenation is described. Copper supported on the carbonaceous support was considered as a catalyst. The reaction of methanol dehydrogenation was thermodynamically conjugated with a reaction of hydrogen oxidation taking place in a shell side of the membrane reactor. The effects of various parameters on the methanol conversion and the methyl formate yield have been calculated with the developed model and discussed. Two different types of heating the gas flow were considered and compared. In the case of conjugated dehydrogenation process, the methyl formate yield reaches 77%, when the reactor outer wall was heated up to 150 °C. When the inlet gas flows in the tube and shell sides were heated up to 100 and 83 °C, correspondingly, the yield was 72%.     

Reaction of 2-methyl-3,4-dihydro-β-carbolin-2-ium iodide with acylmethyl halides controlled by electronic effects: a new route to 1,2-dihydroazepino[4,5-b]indoles

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Preliminary study to prepare a reference material of toluene metabolite – o-cresol and benzene metabolite-phenol – in human urine

The candidate reference material (RM) was prepared by freeze-drying pooled urine samples obtained from healthy persons occupationally exposed to toluene. Homogeneity testing yielded no significant differences of urinary concentrations of o-cresol and phenol in 15 randomly selected units of RM. Stability testing showed no significant changes of concentrations of the above analytes over a period of 6 months. Property (pre-certified) values of phenol and o-cresol concentrations and their uncertainties (9.06±0.47 mg l⁻¹ and 1.03±0.06 mg l⁻¹, respectively) were estimated from results of a small-scale interlaboratory comparison in which two laboratories participated using four different analytical methods.     

Development of Methods of Synthesis of Volatile Organogallium and Organoindium Compounds Used to Prepare Semiconductors

Three new methods for large scale synthesis of electronic grade trimethylgallium and trimethylindium are presented. These methods are based on direct synthesis of trialkylgallium compounds from the Ga/Mg alloy or the mixture of this metals and alkyl halides, RX. The first method consists in the cleavage of the stable trimethylgallium-diethyl ether adduct by heating it in the mixture with ether of higher boiling point. The second one is the reaction of the mixture of Ga and Mg with methyl iodide in a high boiling ether solvent such as diisoamyl ether, i-Am₂O. The third method consist in preliminary formation of the stable adducts of trimethylgallium or trimethylindium and alkali metal fluorides from their etherates, followed by removing ethers and thermal decomposition of adducts to yield free trimethylgallium or trimethylindium respectively.     

Synthesis and X-Ray Crystal Structure of Two Novel Complexes: [M II(phen)3]2V4O12·phen·22H2O(M II=Co, Ni; phen=phenanthroline)

Summary. Two novel compounds, [Co(phen)₃]₂V₄O₁₂·phen·22H₂O (1) and [Ni(phen)₃]₂ V₄O₁₂·phen·22H₂O (2), were prepared from KVO₃–1,10-phenanthroline (phen)–Co(NO₃)₂, resp. NiCl₂–H₂O reaction systems. The compounds 1 and 2 are isomorphous and crystallize in triclinic system, space group P-1. Their crystal structures are formed by two types of layers parallel to 001: a cationic one consisting of [M^II(phen)₃]²⁺ ions and an anionic one containing the cyclic V₄O₁₂ ^4– anions. The solvate phenanthroline and crystal water molecules are located in the cationic and anionic layers, respectively. The IR spectra of 1 and 2 are consistent with the presence of the cyclic V₄O₁₂ ^4– anions in the complexes.Received November 13, 2002; accepted (revised) February 3, 2003 Published online June 2, 2003