From cyclopentadiene to isoxazoline-carbocyclic nucleosides: a rapid access to biological molecules through nitrosocarbonyl chemistry

A rapid access to carbocyclic nucleosides containing a fused isoxazoline ring is proposed starting from cyclopentadiene. The route involves an hetero Diels-Alder cycloaddition reaction of nitrosocarbonylbenzene followed by a 1,3-dipolar cycloaddition of nitrile oxides, cleavage of the N-O tether and elaboration of the heterocyclic aminols into nucleosides via linear construction of purine and pyrimidine heterocycles.     

Electrochemically induced formation of organomercury compounds

A procedure for the alkylation of metallic mercury by (dimethylglyoximato)butylcobalt(III) electrochemically generated in the presence of butyl bromide is proposed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 309–312, February, 1994.     

Magnetic phase transitions in nanostructures induced by shear stress under high pressure

Magnetic phase transitions of the first and second order were revealed by Mössbauer spectroscopy in nanosystems of - and -ferric oxides and metallic europium subjected to shear stress (240°) under high pressure (20 kbar). For - and -ferric oxide nanoclusters, the Curie (Neel) points decreased to 300 K, whereas for nanostructured europium the Neel point increased from 90 to 100 K. The thermodynamic model of magnetic phase transitions predicting a change in the character of magnetic phase transitions and a decrease (increase) in the critical Neel (Curie) points in nanoclusters was developed. The type of magnetic phase transitions and the change in the critical points were caused by defects in nanoclusters, whose maximum concentration was observed for the clusters with the 20—50 nm size range.     

Synthesis and photoluminescence properties of 8-hydroxyquinoline derivatives and their metallic complexes

Three new 8-hydroxyquinoline derivatives, i.e. 5-[(4-styryl-benzylidene)-amino]-quinolin-8-ol (1), 5-[(4-bromo-2-fluoro-benzylidene)-amino]-quinoline-8-ol (2) and 2-[2-(9-ethyl-9H-carbazol-2yl)-vinyl]-quinolin-8-ol (3), and their metallic complexes were synthesized and identified by ultraviolet-visible (UV-Vis), ¹H nuclear magnetic resonance (¹H NMR), Fourier transform infrared spectrometer (FTIR), mass spectrometry (MS) spectra and elemental analyses. Their fluorescence properties were studied by photoluminescence, which indicated that the luminescence wavelength of 5-and 2-substitued-8-hydroxyquinoline derivatives shifted to red in comparison with that of 8-hydroxyquinoline. Meanwhile, the fluorescence lifetime of 2-[2-(9-ethyl-9H-carbazol-2yl)-vinyl]-quinolin-8-ol and its zinc complex showed long lifetime in benzene solution. __________ Translated from Chinese Journal of Organic Chemistry, 2007, 27(3): 402–408 [译自: 有机化学]     

Au/CeO2/Y和Au-MFe2O4催化剂用于有氧条件下CH4还原NOx的研究

以CeO2／Y分子筛和MFe2O4(M=Ni,Co，Zn)为载体，制备Au／CeO2／Y和Au-MFe2O4负载型金催化剂．用CH4做还原剂，考察了它们在有氧条件下催化还原NOχ的活性．结果表明：在Au-Y中引人助剂Ce，使得Au／CeO2／Y的催化活性高于Au／Y；Au-CoFe2O4的催化活性高于Au-Fe2O3，反应温度为300℃时，NOχ在Au-CoFe2O4上的转化率达到39．70%．     

On Mercury(I) Oxo Compounds — Quasi‐Relativistic Computational and Experimental Studies

About 60 molecular species composed of up to 10 mercury atoms and of oxygen atoms and/or of some other elements or groups (such as halogen, OH₂, OH, H, alkali, NO₃) have been investigated quantum chemically. Different density functional approaches and the ab initio SCF‐MP2 method were applied, comparing different basis sets and different atomic core sizes. It is important not to treat the Hg 5s, p, d as inactive core shells, and to use sufficiently many polarization functions. The shape of the 〉O‐Hg‐Hg‐O〈 units is not favorable concerning the formation of lattices composed of Hg^I, O and OH only. Despite its bulkiness, the OHgHgO units can easily come into contact with each other and then disproportionate. This is prevented in the so‐called ternary M‐Hg^I oxides by the embedded oxometallate (oxoacidic) anions. Furthermore, the Hg^I and Hg^II oxide bond energies are less favorable towards the stability of Hg^I oxo compounds, as compared to Hg halidic or oxoacidic compounds. Both points are not promising concerning the search for Hg^I oxides/hydroxides, although the preparation of such compounds, including spacer groups, by topochemical reactions can still not be excluded. So far, experimental efforts towards the synthesis of such a new class of compounds have only demonstrated that Hg^II is strictly preferred over Hg^I in the formation of solids of binary Hg‐O or ternary A‐Hg‐O composition (A = electropositive metal such as alkali, in contrast to M = transition or semi‐metal). This is so even if compounds containing ‘electron rich Hg^δ— atoms’ (i.e. A‐Hg amalgams) are oxidized under mild conditions.     

Influence of the texture of chromia catalysts on their activity in synthesis of 2-methylthiophene

The texture of Cr₂O₃-K₂O/Al₂O₃catalysts containing oxides of rare earth elements (REE) was studied. The catalysts are used for the synthesis of 2-methylthiophene by the reaction of H₂S with n-pentane or piperilene. The heterocyclization of n-pentane is a consecutive reaction involving a step of dehydrogenation of initial hydrocarbon. At this step the texture of the catalyst affects the yield of 2-methylthiophene. The yield of 2-methylthiophene obtained from piperilene and I₂S is independent of the catalyst texture.     

Preparation of Mn3O4 nanocrystallites by low-temperature solvothermal treatment of γ-MnOOH nanowires

The preparation of trimanganese tetroxide (Mn₃O₄) nanocrystallites from γ-MnOOH nanowires under mild conditions has been achieved by two steps: first, γ-MnOOH nanowires with a mean diameter of about 12 nm and lengths of up to several micrometers were directly prepared via hydrothermal reaction between KMnO₄ and toluene in water at 180°C for 24 h; then, pure Mn₃O₄ nanocrystallites could be obtained by solvothermal treatment of the γ-MnOOH nanowires in ethylenediamine (EDA) and ethylene glycol (EG) at 150°C for 24 h. It was found that the Mn₃O₄ product obtained in EDA comprised well-defined nanocrystallites with the size in the range of 15-35 nm, while the one obtained in EG consisted of aggregated nanoparticles with the size of less than 18 nm.The possible formation mechanism of nanocrystalline Mn₃O₄ in EDA and EG and reasons for the different effects of various solvents on the products were also proposed.     

Synthesis, structure and magnetic properties of the S=1/2, one-dimensional antiferromagnet, Y5Re2O12

Single crystals of Y₅Re₂O₁₂ have been grown, and the crystal structure has been determined by X-ray diffraction. This compound crystallizes in space group C2/m with cell dimensions of a=12.4081(10) Å b=5.6604(5)Å, c=7.4951(6) Å, β=107.837(3)°, Z=2. The final refinement led to R1=0.0238, WR2=0.0459 for 1053 observed reflections with F>4σ(F₀). Edge-sharing ReO₆ octahedra form infinite linear [ReO₂O_4/2]_n chains along the b direction with alternating short and long Re-Re distances. Three crystallographically independent yttrium atoms surround O2 to form OY₄ tetrahedra, which share edges and corners in the ab plane to form a two-dimensional Y₅O₄ network which separates the [ReO₂O_4/2]_n magnetic chains. This compound is therefore isostructural with the series Ln₅Re₂O₁₂Ln=Gd-Lu, which have been known since 1969. The average Re oxidation state is +4.5 in the chains and a reasonable, if qualitative MO scheme results in one unpaired electron per Re dimer. Consistent with this, magnetic susceptibility data can be fitted to the one-dimensional antiferromagnetic Heisenberg model with S=1/2 and parameters J^intra/k=−89(1)K, g=2.15(4) and χ(TIP)=5(1)×10⁻⁴ emu/mol. There is no sign of long-range magnetic order down to 2 K. These results are contrasted with those for the isostructural Y₅Mo₂O₁₂.     

Novel reaction of 1-aryl-2-bromodiazene 1-oxides with olefins. Synthesis of 1-aryl-2-(2-bromoalkyl)diazene 1-oxides

The addition of 1-aryl-2-bromodiazene 1-oxides to olefins yields 1-aryl-2-(2-bromoalkyl)diazene 1-oxides (4). A radical mechanism of the reaction has been suggested. Compounds4 decompose to give bromohydrazones of formaldehyde and aldehydes. The structural factors that affect the rate of this process are discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 917–923, May, 1995.The work was carried out in the Scientific Educational Center of the Institute of Organic Chemistry of the RAS with financial support of the Russian Foundation for Basic Research (Project No. 93-03-18461).