Polyfunctional pyrazoles. 4. Synthesis of 3-[3-aryl-1-(2-ethoxycarbonyl)-4-pyrazolyl]acrylic and-propionic acids

3-(3-Aryl-4-formyl-1-pyrazolyl)propionic acids are converted by Knoevenagel condensation under conditions of microwave activation into 3-[3-aryl-1-(2-ethoxycarbonyl)-4-pyrazolyl]acrylic acids. Reduction of the latter with hydrazine hydrate in the presence of Raney nickel gives 3-[3-aryl-1-(2-ethoxycarbonyl)-4-pyrazolyl]propionic acids. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 686–690, May, 2006.     

[COH(NH2)2]2[Cu(pic)2(ClO4)2]的合成与晶体结构

The title compound was synthesized by reaction of Cu(ClO₄)₂， picolinic acid and carbamide in C₂H₅OH/CH₃CN solution， and characterized by single-crystal X-ray diffraction. It crystallizes in the orthorhombic system， space group Pbca with a=14.0481(8)， b=9.0130(5)， c=18.626(1)?， V=2358.3(2)?³， Z=4， D_x=1.771g·cm^-3， μ=1.235mm^-1 and F(000)=1276. The final R factor is 0.0440 for 1434 observed reflections. The X-ray analysis revealed that the copper(Ⅱ) atom is coordinated by two picolinic ligands in the equatorial plane， while the two oxygen atoms of perchlorate occupy the axial positions of octahedron with lengthened Cu-O distances， resulting in a 4+2 elongated octahedral environment. In the compound， there also exist two protonated carbamide cations for charge balance. CCDC： 195354.     

Construction of a pyrido[4,3-<Emphasis Type="Italic">d</Emphasis>]pyrimidine system on the basis of <Emphasis Type="Italic">N</Emphasis>-cyanobenzamidine and diethyl acetone-1,3-dicarboxylate

Nickel acetate promoted reaction of diethyl acetone-1,3-dicarboxylate with N-cyanobenzamidine led to ethyl 4-amino-6-ethoxycarbonylmethyl-2-phenylpyrimidine-5-carboxylate, upon treatment of which with RNH₂, the corresponding 6-(carbamoylmethyl)pyrimidines were obtained. Cyclization of the latter upon treatment with MeONa afforded 6-R-4-amino-7-hydroxy-2-phenylpyrido[4,3-d]pyrimidin-5(6H)-ones. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2212–2214, November, 2007.     

Formation of different products during photo-catalytic reaction on TiO<Subscript>2</Subscript> suspension in water with and without 2-propanol under diverse ambient conditions

Studies on photo-catalytic reduction of CO₂ using TiO₂ photo-catalyst (0.1%, w/v) as a suspension in water was carried out at 350 nm light. CO₂ from both commercially available source, as well as generated in situ through 2-propanol oxidation, was used for this study. The photolytic products such as hydrogen (H₂), carbon monoxide (CO) andmethane (CH₄) generated were monitored in TiO₂ suspended aqueous solution with and without a hole scavenger, viz., 2-propanol. Similar photolytic experiments were also carried out with varying ambient such as air, O₂, N₂ and N₂O. The yields of CO and CH₄ in all these systems under the present experimental conditions were found to be increasing with light exposure time. H₂ yield in N₂-purged systems containing 2-propanol was found to be more as compared to the without 2-propanol system. The rate of H₂ production in N₂-purged aqueous solutions containing 0.1% TiO₂ suspension were evaluated to be 0.226 and 5.8 μl/h, without and with 0.5 M 2-propanol, respectively. This confirmed that 2-propanol was an efficient hole scavenger and it scavenged photo-generated holes (h⁺), allowing its counter ion, viz., e⁻, to react with water molecule/H⁺ to yield more H₂. The formation of both CO and CH₄ in the photolysis of CO₂-purged aqueous solutions containing suspended TiO₂ in absence of 2-propanol reveal that the generation of CH₄ is taking place mainly through CO intermediate. In presence of air/O₂, the yield of H₂ in the system without 2-propanol was observed to be negligible as compared to the system containing 2-propanol in which low yield of H₂ was obtained with a formation rate of approx. 0.5 μl/h.     

Crystal and molecular structures of binuclear caesium complexes with 1,3-calix[4]-bis-crown-6 and 1,3-calix[4]-bis-benzo-crown-6

The crystal structures of two binuclear complexes between caesium and 1,3-calix[4]-bis-crowns have been determined. Cs₂ Bis-benzoC6(NO₃)₂. 3CHCl₃ (1) in whichBis-benzoC6 is 1,3-calix[4]-bis-benzo-crown-6, crystallizes in the orthorhombic system: space groupPca2 ₁ a=19.513(10),b=15.382(5),c=23.708(9) Å,V=7116(5) ų,Z=4. Refinement led to a final conventionalR value of 0.065 for 2321 reflections. The structure of (1) is analogous to those already reported withBis-C6, (in whichBis-C6 is, 1,3-calix[4]-bis-crown-6) and NO ₃ ^– as a counter-ion. Cs₂ Bis-C6(NCS)₂ (2) crystallizes in the monoclinic system: space, groupC2 a=36.57(2),b=11.47(1),c=13.65(1) Å, =109.03(5)°.,V=5415(6) ų,Z=4. Refinement led to a final conventionalR value of 0.063 for 2227 reflections. Compound (2) is made of dimers bridged by a disordered NCS^– ion. The crown ether chain conformations are discussed. Supplementary data relating to this article (atomic coordinates, anisotropic displacement parameters, bond distances and angles and observed and calculated structure factors) are deposited with the British Library as Supplementary Publication No. SUP 82199 (52 pages).     

Ein neues Samariumnitridsulfid: Sm4N2S3

A New Samarium Nitride Sulfide: Sm₄N₂S₃ The oxidation of samarium with sulfur in the presence of SmCl₃ and NaN₃ as nitrogen source (molar ratio: 12:9:4:2, evacuated silica vessel, some NaCl as flux, 850°C, 7 d) yields Sm₄N₂S₃ as lath-shaped, dark red single crystals. The by-products (NaCl and NaSm₂Cl₆) are rinsed with water from the crude product. The crystal structure of Sm₄N₂S₃ (monoclinic, C2/m (no. 12), Z = 2, a = 1 318.04(12), b = 391.57(2), c = 1 031.76(9) pm, β = 130.874(6)°, R = 0.036, R_w = 0.031) contains two crystallographically different Sm³⁺, both in sixfold coordination of the anions. Besides distorted octahedra [(Sm1)N₃S₃] and [(Sm2)NS₅], tetrahedra [(N^3?)(Sm)] connected via two cis-oriented edges to form chains [N(Sm1)_3/3(Sm2)_1/1]³⁺ build up the Mayn structural feature. These are arranged in the fashion of a closest packing of rods and held together by two crystallographically different S^2? anions which take care for charge neutrality and three-dimensional interconnection.     

Das erste Diniobat mit ‚isolierten’︁ Anionen: KLi4[NbO5]=K2Li8[Nb2O10]

The First Diniobate with ‘Isolated’ Anions: KLi₄[NbO₅]=K₂Li₈[Nb₂O₁₀] [1] . By heating of well ground mixtures of the binary oxides [K₂O, Li₂O, Nb₂O₅, K:Li:Nb=1.1:4.4:1, Pt-tube, 1100°C, 3d] colourless, triclinic single crystals of KLi₄NbO₅ have been prepared for the first time: space group P1 (Nr. 2) with a=816.9(2) pm, b=592.2(2) pm, c=589.7(2) pm, α=121.00(2)º, β=91.78(2)°, γ=99.23(2)°, Z=2. The crystal structure was solved by four-cycle diffractometer data [Mo-Kα , 1386 from 1386 I_o(hkl), R=3.4%, R_w=2.6%], parameters see text. Characteristic for this structure are “isolated” groups of [Nb₂O₁₀] and the tetrahedral coordination of Li(1), Li(2), and Li(3). Li(4) has a tetragonal-pyramidal coordination. The structural relations are deduced by Schlegel Diagrams. The Madelung Part of Lattice Energy, MAPLE, the Effective Coordination Numbers, ECoN and the charge distribution have been calculated and discussed.     

Zinc(II) Hydration in Aqueous Solution: A Raman Spectroscopic Investigation and An ab initio Molecular Orbital Study of Zinc(II) Water Clusters

Raman spectra of aqueous Zn(II)–perchlorate solutions were measured over broad concentration (0.50–3.54 mol-L^–1) and temperature (25–120°C) ranges. The weak polarized band at 390 cm^–1 and two depolarized modes at 270 and 214 cm^–1 have been assigned to ₁(a _1g), ₂(e _g), and ₅(f _2g) of the zinc–hexaaqua ion. The infrared-active mode at 365 cm^–1 has been assigned to ₃(f _1u). The vibrational analysis of the species [Zn(OH₂) ₂ ⁺ ] was done on the basis of O _h symmetry (OH₂ as point mass). The polarized mode ₁(a _1g)-ZnO₆ has been followed over the full temperature range and band parameters (band maximum, full width at half height, and intensity) have been examined. The position of the ₁(a _1g)-ZnO₆ mode shifts only about 4 cm^–1 to lower frequencies and broadens by about 32 cm^–1 for a 95°C temperature increase. The Raman spectroscopic data suggest that the hexaaqua–Zn(II) ion is thermodynamically stable in perchlorate solution over the temperature and concentration range measured. These findings are in contrast to ZnSO₄ solutions, recently measured by one of us, where sulfate replaces a water molecule of the first hydration sphere. Ab initio geometry optimizations and frequency calculations of [Zn(OH₂) ₂ ⁺ ] were carried out at the Hartree–Fock and second-order Møller–Plesset levels of theory, using various basis sets up to 6-31 + G*. The global minimum structure of the hexaaqua–Zn(II) species corresponds with symmetry T _h. The unscaled vibrational frequencies of the [Zn(OH₂) ₂ ⁺ ] are reported. The unscaled vibrational frequencies of the ZnO₆, unit are lower than the experimental frequencies (ca. 15%), but scaling the frequencies reproduces the measured frequencies. The theoretical binding enthalpy for [Zn(OH₂) ₂ ⁺ ] was calculated and accounts for ca. 66% of the experimental single-ion hydration enthalpy for Zn(II).Ab initio geometry optimizations and frequency calculations are also reported for a [Zn(OH₂) ₂ ¹⁸ ] (Zn[6 + 12]) cluster with 6 water molecules in the first sphere and 12 in the second sphere. The global minimum corresponds with T symmetry. Calculated frequencies of the zinc [6 + 12] cluster correspond well with the observed frequencies in solution. The ₁-ZnO₆ (unscaled) mode occurs at 388 cm^–1 almost in perfect correspondence to the experimental value. The theoretical binding enthalpy for [Zn(OH₂) ₂ ¹⁸ ] was calculated and is very close to the experimental single ion-hydration enthalpy for Zn(II). The water molecules of the first sphere form strong hydrogen bonds with water molecules in the second hydration shell because of the strong polarizing effect of the Zn(II) ion. The importance of the second hydration sphere is discussed.     

Stereoselective synthesis of (3R,4S,5S,9S)-3,5,9-trihydroxy-4-methylundecanoic acid δ-lactone

A stereoselective synthesis of the pentaketide lactone (3R,4S,5S,9S)-3,5,9-trihydroxy-4-methylundecanoic acid δ-lactone has been achieved.