Effect of H2S-uptake on the conversion of cyclohexene on Ru- and Pd-promoted molybdena-alumina catalysts

The effect of H₂S on the activity and selectivity of catalysts (Ru/Al₂O₃, Pd/Al₂O₃ and Ru and Pd promoted molydena-alumina) was different (on differnt catalysts and different conversions of cyclohexene). Ru-containing catalysts showed higher sulfur sensitivities than the Pd-containing ones. The sequence of catalysts by their H₂S uptake related to mass of catalyst was PdMo/Al₂O₃RuMo/Al₂O₃Mo/Al₂O₃>Pd/Al₂O₃Ru/Al₂O₃.     

Triterpene glycosides from Pulsatilla chinensis

Four triterpene glycosides were isolated from the roots of Pulsatilla chinensis (Bunge) Regel (Ranunculaceae). Two new glycosides, chinensiosides A (1a) and B (2), were identified as 3-O-[-L-rhamnopyranosyl-(12)--L-arabinopyranosyl]-28-O-[-L-rhamnopyranosyl-(14)--D-glucopyranosyl-(16)--D-glucopyranosyl]-3,23-dihydroxylup-20(29)-en-28-oic acid and 3-O-{-L-rhamnopyranosyl-(12)-[-D-glucopyranosyl-(14)]--L-arabinopyranosyl}-28-O-[-L-rhamnopyranosyl-(14)--D-glucopyranosyl-(16)--D-glucopyranosyl]-3,23-dihydroxylup-20(29)-en-28-oic acid. The other two glycosides were identified as previously known hederasaponin C (3) from Hedera helix and glycoside III (4) from Pulsatilla cernua.     

Steroid polyols from the Far-Eastern starfish Henricia sanguinolenta

A new polyhydroxylated steroid (20R,24S)-5-cholestane-3,6,15,24-tetraol and a known glycoside, laeviuscoloside G, was isolated from the Far-Eastern starfish Henricia sanguinolenta, collected in the sea of Okhotsk, and characterized.     

Electrode kinetics and thermodynamic study of complexes of palladium(II) at D.M.E.

Polarographic study of Pd(II) reveals that it reduces quasireversibly at d.m.e. in 0.2M-pyridine+0.1N-HCl medium. Kinetic parameters of Pd(II) in various concentrations of -resorcyclic acid were calculated usingGellings method and thus the effect of concentration of -resorcyclic acid on the kinetics of the reduction of Pd(II) has been explained.DeFord/Hume graphical extrapolation method and the mathematical method ofMihailov have been employed for the evaluation of overall formation constants of the complexes formed with -resorcyclic acid. The logarithmic values of overall formation constants ₁, ₂ and ₃ obtained by the two methods are 7.47, 8.60, 9.66 (DeFord andHume Method) and 7.44, 8.64, 9.66 (Mihailov Method) at 298 K. Thermodynamic parameters of these complexes are reported.

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Elektrodenkinetik und thermodynamische Untersuchungen an Pd(II)-Komplexen mittels polarographie

Zusammenfassung Pd(II) zeigt eine quasireversible Reduktion in 0,2M-Pyridin/0,1N-HCl. Kinetische Parameter wurden mittels der Methode vonGelling ermittelt und damit der Effekt verschiedener -Resorcylsäurekonzentrationen erklärt. Bildungskonstanten der entsperechenden Komplexe wurden nachDeFord/Hume und nachMihailov ermittelt. Die logarithmischen Werte der Gesamtbildungskonstanten ₁, ₂ und ₃ bei 298 K betragen nach derDe Ford/Hume-Methode 7,47, 8,60 und 9,66, nach derMihailov-Methode 7,44. 8,64 und 9,66. Die thermodynamischen Parameter der Komplexbildung werden angegeben.

     

A new steroidal glycoside phrygioside A and its aglycone from the starfish <Emphasis Type="Italic">Hippasteria phrygiana</Emphasis>

Three polyhydroxylated steroids were isolated from the Far-Eastern starfish Hippasteria phrygiana collected from the Sea of Okhotsk and were characterized as a new glycoside phrygioside A, viz., sodium (20R, 24S)-3,4,7,8,15,24-hexahydroxy-24-O-[3-O-methyl--D-xylopyranosyl-(12)--L-arabinofuranosyl]-5-cholestan-6-yl sulfate, its aglycone, and the already known marthasterone sulfate.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2526–2529, November, 2004.     

Complex polarizability as used to analyze dielectric relaxation measurements

The effect of representing dielectric properties in terms of the complex polarizability ^c = – i is examined. Loss curves ( and tan ) are shifted towards higher frequencies, revealing the existence of new relaxations and allowing the clarifications of ones already known. We have calculated the shift ratios (at maximum or tan )/ (at maximum or tan ) from the more conventional empirical equations representing the dielectric behavior. Some examples are given.     

Studies on the Complexes of N,N′-Bis[o-(diphenylphosphino)benzylidene]ethylenediamine with Transition Metal Ions

The thermodynamic parameters for the interaction of Cu²⁺, Ni²⁺, Co²⁺, Cd²⁺, andAg⁺ with the new title ligand have been determined by titration calorimetry in 50% THF–methanol (V/V) at 25 °C.Ag⁺ exhibited remarkably higher complexation selectivity.Ag⁺ and several transition metal ions have been transportedusing this ligand as carrier in a bulk liquid membrane. CompetitiveAg⁺–M²⁺ transport studies have also beencarried out for the same system. In this membrane transport study, high transport of Ag⁺ was observed in both single and competitiveAg⁺–M²⁺ transport studies. The complexformation of N,N-bis[o-(diphenylphosphino)benzylidene]ethylenediamine (P₂N₂) with silver,[Ag(P₂N₂)] (NO₃), (1) is reported. Complex 1 has been characterized by X-ray crystallography. 1 ismonoclinic, space group P2_1/n (No. 14), with cell dimensionsa = 13.398(4) , b=12.577(5) , c = 21.521(4) , =100.14(2) , V = 3570(2) ³ and Z = 4.     

13-Acetoxy-heptadecadien-(8, 10)-ol-(1), Octadien-(3, 5)-ol-(1)-Isomere und verwandte Verbindungen

Zusammenfassung Es werden diecis,cis- undtrans,trans-Isomeren der primären Alkohole Octadien-(3,5)-ol-(1) (I), 15-Acetoxy-nonadeca-dien-(10,12)-ol-(1) (IV), 17-Acetoxy-heneikosa-dien-(10,12)-ol-(1) (V), 12-Acetoxy-pentadeca-dien-(8,10)-ol-(1) (VII) und 13-Acetoxy-heptadeca-dien-(8,10)-ol-(1) (VI) synthetisiert und zusammen mit einigen Zwischenprodukten und Analogen unter Verwendung des Seidenspinners (Bombyx mori L.) und des Schwammspinners (Lymantria dispar L.) auf Attraktivität getestet. DieL. E.-Werte der synthetisierten cis,cis-VI-Präparate liegen in der Größenordnung von 10^–9 g/ml.

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Thecis, cis- andtrans, trans-isomere of the primary alcohols octadien-(3,5)-ol-(1) (I), 15-acetoxy-nonadecadien-(10,12)-ol-(1) (IV), 17-acetoxy-heneicosadien-(10,12)-ol-(1) (V), 12-acetoxypentadecadien-(8,10)-ol-(1) (VI) have been synthesized and tested for effectiveness as attractant together with several intermediates and analogues using the Silk Moth (Bombyx mori L.) and the Gipsy Moth (Lymantria dispar L.) The values of the attractant units of the cis, cis-VI-compounds synthesized are of the order 10^–9 g/ml.

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4. Mitt. der Reihe Synthese und Wirksamkeit von Sexualduftstoff-Analogen; 3. Mitt.:R. Riemschneider, A. Kühnl undK. Brockmeyer, unveröffentlichte Versuche; 2. Mitt.:R. Riemschneider undG. Kasang, Z. Naturforschg.18 b, 646 (1963); 1. Mitt.:R. Riemschneider, Vortrag vom 1. 9. 1962 in S. Paolo.     

Adsorption behavior of polymers having phosphoric acid group on γ-Fe2O3 and magnetic characteristics in magnetic coatings

Polymers having phosphoric acid groups were prepared as a model binder for magnetic coatings, and the correlation among the adsorption behavior of the polymers onto-Fe₂O₃ particles and the dispersibility, the orientation, and the packing density of-Fe₂O₃ particles in the magnetic coatings was investigated.PMMA homopolymer molecules hardly adsorbed on-Fe₂O₃, and the interfacial tension at a water/polymer solution (toluene) interface ( _W/T) was scarcely changed compared with a water/toluene interface. Increasing with the content of polymeric phosphoric acid group, the adsorbance of polymer increased and the interfacial tension ( _W/T) decreased. When the content of polymeric phosphoric acid groups was over 0.4 mol%, the adsorbance of polymer and interfacial tension ( _W/T ) remained constant. When these polymers were used as a binder for magnetic tapes, the dispersibility of-Fe₂O₃ in the magnetic coatings was improved, increasing with the content of polymeric phosphoric acid group; however, when the content of phosphoric acid group was over 0.2 mol%, its dispersibility decreased abruptly.Studies on Recording Magnetic Materials and Magnetic Composite. XVIII.     

Non-equilibrium ion-(polar) molecule reaction rate coefficients

Using the Fokker-Planck version of an approximate Boltzmann equation for the ion (translational) energy distribution function f_I we have calculated the deviation, k, of the non-equilibrium ion-(polar)molecule reaction rate coefficient k (based) on f_I from its equilibrium value k⁽⁰⁾. The _D (dipole moment)-dependence of the reaction cross section applied leads to a corresponding dependence of k on _D.

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- , k - ( f_I) k⁽⁰⁾. k _D.

     

Triterpene Glycosides of Fatsia japonica. VI. Structures of Glycosides D3a and D3b

Seeds of Fatsia japonica (Araliaceae) yielded the new glycosides of gypsogenin: 3-O--D-glucopyranosyl-(12)-O--D-glucopyranoside and 3-O--D-galactopyranosyl-(12)-O--D-glucopyranoside. The structures of these compounds were established by chemical methods and NMR spectroscopy.     

Composite Pd/Pr4O7/C catalysts: Synthesis, dispersity and properties

The catalysts prepared sequentiallyvia the interaction of C₃H₅PdC₅H₅ with the surface of evacuated Pr₄O₇/C and reduction with H₂ at 573 K, contain 20–30 Pd particles and Pr₄O₇ particles<20 . The catalysts obtained have two-order of magnitude higher specific activity in the CH₃OH synthesis than Pd/C.     

Hochtemperatur-röntgenographische Untersuchungen an manganreichen Mangan—Vanadin-und Mangan—Chrom—Legierungen

Zusammenfassung Die manganreiche Seite der Systeme Mn–V und Mn–Cr wurde hochtemperatur-röntgenographisch untersucht. Im System Mn–V treten bei 90 At% Mn zwei bisher nicht beobachtete Phasen, und , mit -bzw. -Manganstruktur auf. Diese gehören möglicherweise der Klasse der -bzw. -Phasen an. Die -Mischphase besitzt einen größeren Existenzbereich als in der Literatur angegeben. Die Existenz der -Phase Mn₃V, sowie die Phasenzustände bis 80 At% Mn und bei manganreicheren Legierungen unterhalb 700°C werden bestätigt. Das lineare thermische Ausdehnungsverhalten der Phasen , und sowie des -und -Mischkristalls werden angegeben. Für den manganreichen Teil wird ein vorläufiges Zustandsdiagramm entworfen. Im System Mn–Cr konnte in großen Zügen Über-einstimmung mit Literaturangaben gefunden werden. Es wird das lineare thermische Ausdehnungsverhalten der -Phase Mn₃Cr angegeben.

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High temperature X-ray investigation of Mn—rich Mn—V and Mn—Cr alloys

The manganese rich portions of the phase diagrams Mn–V and Mn–Cr have been investigated by means of a high temperature X-ray technique. In the system Mn–V two new phases, and , have been observed with -manganese and -manganese type structure, resp. These phases are probably to be classified as -and -phase. The -manganese solid solution with vanadium has a wider range of homogeneity as compared with previous work. The existence of a -phase Mn₃V and phase equilibria below 700°C reported previously could be confirmed. The linear thermal expansion of the intermetallic compounds , , , the -and -manganese solid solutions with vanadium has been evaluated. A tentative phase diagram for the manganese rich portion is given. The main features of the system Mn–Cr according to previous investigations could be confirmed. The linear thermal expansion of the -phase Mn₃Cr is reported.

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Mit 8 Abbildungen

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Herrn Prof. Dr.Hans Nowotny in Dankbarkeit gewidmet.     

Comparison of the crystal structures of Co2(X 2O7)·2H2O,X=P and As

Summary Crystals of Co₂(X ₂O₇)·2H₂O,X=P/As were synthesized under hydrothermal conditions. Their crystal structures were determined by single crystal X-ray diffraction:a=6.334(1)/6.531(2),b=13.997(2)/14.206(4),c=7.637(1)/7.615(2)Å, =94.77(2)/94.74(2)°, space group P2₁/n,R=0.032/0.046,R _w=0.028/0.034 for 2423/2042 reflections and 131/119 variables. Within the twoXO₄ tetrahedra connected via a common corner to anX ₂O₇ group the average P-O bond lengths are approximately equal (1.540 and 1.543 Å), but As-O differs significantly (1.685 and 1.696 Å). A comparison with the isotypic Mn and Mg pyrophosphates shows a correlation between the ratio Me-O/X-O and the angle O-X-O.

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Vergleich der Kristallstrukturen von Co₂(X ₂O₇)·2H₂O,X=P und As

Zusammenfassung Kristalle von Co₂(X ₂O₇)·2H₂O,X=P/As wurden unter Hydrothermalbedingungen synthetisiert. Ihre Kristallstrukturen wurden mittels Röntgenbeugung an Einkristallen bestimmt:a=6.334(1)/6.531(2),b=13.997(2)/14.206(4),c=7.637(1)/7.615(2) Å, =94.77(2)/97.74(2)°, Raumgruppe P2₁/n,R=0.032/0.046,R _w=0.028/0.034 für 2423/2042 Reflexe und 131/119 Variable. In den beiden über eine gemeinsame Ecke zuX ₂O₇-Gruppen verknüpftenXO₄-Tetraedern sind die mittleren P-O-Abstände ungefähr gleich (1.540 und 1.543 Å), hingegen differiert As-O signifikant (1.685 und 1.696 Å). Ein Vergleich mit den isotypen Mn- und Mg-Pyrophosphaten zeigt eine Korrelation zwischen dem Quotienten Me-O/X-O und dem WinkelX-O-X.

     

Optisch aktive,aromatische Spirane, 11. Mitt.: Synthese optisch aktiver mono- bis heptasubstituierter 5-Methyl- und 5-Ethyl-2,2′-spirobiindane und analoger Naphthalinderivate bekannter Chiralität und enantiomerer Reinheit

Starting from optically active 5,5-dimethyl, diethyl, and 5-ethyl-5-methyl-2,2-spirobiindane as well as from 5-ethyl-spirobiindane-5-carboxylic ester of known enantiomeric purity and configuration 75 mono to polysubstituted 2,2-spirobiindanes have been prepared. Amongst these are several compounds with rings anellated in the 6,7 (and 6, 7) positions, especially a spirohydrocarbon4 x with orthogonal naphthalene units the circular dichroism of which is reported and discussed.Several mono and disubstituted 5-methyl and ethylindanes (1,2) have been prepared as models for synthetic transformations in the spirobiindane series.From the molar rotations of symmetrically diacylated 5,5-dimethyl and diethyl spirobiindanes (4a, 7b, 7c) empirical ligand parameters for acetyl and methoxycarbonyl were determined which gave much better results in the calculation of the rotations of appropriate spirobiindanes (with the shortened polynomal Ansatz) than the -values deduced previously from 5,5-disubstituted spirobiindanes. The significance of these results is briefly discussed.

10. Mitt.:Neudeck, H., Schlögl, K., Angew. Chem.92, 318 (1980), Intern. Ed. Engl.19, 308 (1980).     

Thermal ignition studies on metallized fuel-oxidizer systems

The thermal ignition behaviour of various mixtures of organic fuels, magnesium and ammonium nitrate (AN) has been examined by differential thermal analysis technique. It has been observed that the thermal decomposition/ignition of organic fuel-AN mixtures is modified significantly in the presence of magnesium metal. The decomposition characteristics of the binary mixtures of AN with various metals indicate the specific action of magnesium and zinc in lowering the decomposition temperature. A possible explanation for the low temperature decomposition is given in terms of the solid state reaction causing the fusion of AN which further reacts with the metal resulting in a highly exothermic reaction.

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Zusammenfassung Mittels DTA wurde das thermische Initiierungsverhalten verschiedener Gemische aus organischen Brennstoffen, Magnesium und Ammoniumnitrat (AN) untersucht. Es wurde festgestellt, daß die thermische Zersetzung/Initiierung von Gemischen aus organischen Brennstoffen und AN durch die Gegenwart von metallischem Magnesium bedeutsam beeinflußt wird. Die Zersetzungscharakteristiken binären Gemische aus AN und verschiedener Metalle zeigen eine spezielle Wirkung von Magnesium und Zink bei der Herabsetzung der Zersetzungstemperatur. Eine mögliche Erklärung für die Zersetzung bei niedrigerer Temperatur kann in Bezug auf die Festkörperreaktion gesehen werden, die das Schmelzen von AN verursacht, welches dann mit dem Metall stark exotherm reagiert.

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, (). , / — . . , , .

     

The complexation of 2,3-anthracenedicarboxylate by β- and γ-cyclodextrins in mixed solvent systems as studied by induced circular dichroism. The role of cosolvent hydrophobicity

The complexation of 2,3-anthracenedicarboxylate (ADC) by- and-cyclodextrins in water containing an organic solvent has been studied by induced circular dichroism. It has been shown that an increase of organic solvent ratio causes the degradation of the 1:1 ADC:-CD complex and the liberation of one guest molecule from the 2:1 ADC:-CD complex in water. The higher the hydrophobicity of the cosolvent, the weaker the complexation of ADC by-CD.     

On the crystal chemistry of three copper(II)-arsenates: Cu3(AsO4)2-III,Na4Cu(AsO4)2, and KCu4(AsO4)3

The three copper(II)-arsenates were synthesized under hydrothermal conditions; their crystal structures were determined by single-crystal X-ray diffraction methods:Cu₃(AsO₄)₂-III:a=5.046(2) Å,b=5.417(2) Å,c=6.354(2) Å, =70.61(2)°, =86.52(2)°, =68.43(2)°,Z=1, space group ,R=0.035 for 1674 reflections with sin / 0.90 Å^–1.Na₄Cu(AsO₄)₂:a=4.882(2) Å,b=5.870(2) Å,c=6.958(3) Å, =98.51(2)°, =90.76(2)°, =105.97(2)°,Z=1, space group ,R=0.028 for 2157 reflections with sin / 0.90 Å^–1.KCu₄(AsO₄)₃:a=12.234(5) Å,b=12.438(5) Å,c=7.307(3) Å, =118.17(2)°,Z=4, space group C2/c,R=0.029 for 1896 reflections with sin / 0.80 Å^–1.Within these three compounds the Cu atoms are square planar [4], tetragonal pyramidal [4+1], and tetragonal bipyramidal [4+2] coordinated by O atoms; an exception is the Cu(2)^[4+1] atom in Cu₃(AsO₄)₂-III: the coordination polyhedron is a representative for the transition from a tetragonal pyramid towards a trigonal bipyramid. In KCu₄(AsO₄)₃ the Cu(1)^[4]O₄ square and the As(1)O₄ tetrahedron share a common O—O edge of 2.428(5) Å, resulting in distortions of both the CuO₄ square and the AsO₄ tetrahedron. The two Na atoms in Na₄Cu(AsO₄)₂ are [6] coordinated, the K atom in KCu₄(AsO₄)₃ is [8] coordinated by O atoms.Die drei Kupfer(II)-Arsenate wurden unter Hydrothermalbedingungen gezüchtet und ihre Kristallstrukturen mittels Einkristall-Röntgenbeugungsmethoden ermittelt:Cu₃(AsO₄)₂-III:a = 5.046(2) Å,b = 5.417(2) Å,c = 6.354(2) Å, = 70.61 (2)°, = 86.52(2)°, = 68.43(2)°,Z = 1, Raumgruppe ,R = 0.035 für 1674 Reflexe mit sin / 0.90 Å^–1.Na₄Cu(AsO₄)₂:a = 4.882(2) Å,b = 5.870(2) Å,c = 6.958(3) Å, = 98.51(2)°, = 90.76(2)°, = 105.97(2)°,Z = 1, Raumgruppe ,R = 0.028 für 2157 Reflexe mit sin / 0.90 Å^–1.KCu₄(AsO₄)₃:a = 12.234(5) Å,b = 12.438(5) Å,c = 7.307(3) Å, = 118.17(2)°,Z = 4, Raumgruppe C2/c,R = 0.029 für 1896 Reflexe mit sin / 0.80 Å^–1.Die Cu-Atome in diesen drei Verbindungen sind durch O-Atome quadratisch planar [4], tetragonal pyramidal [4 + 1] und tetragonal dipyramidal [4 + 2]-koordiniert; eine Ausnahme ist das Cu(2)^{[4 + 1]}-Atom in Cu₃(AsO₄)₂-III: Das Koordinationspolyeder stellt einen Vertreter des Übergangs von einer tetragonalen Pyramide zu einer trigonalen Dipyramide dar. In KCu₄(AsO₄)₃ haben das Cu(1)^[4]O₄-Quadrat und das As(1)O₄-Tetraeder eine gemeinsame O—O-Kante von 2.428(5) Å, was eine Verzerrung der beiden Koordinationsfiguren CuO₄-Quadrat und AsO₄-Tetraeder bedingt. Die zwei Na-Atome in Na₄Cu(AsO₄)₃ sind durch O-Atome [6]-koordiniert, das K-Atom in KCu₄(AsO₄)₃ ist [8]-koordiniert.

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Zur Kristallchemie dreier Kupfer (II)-Arsenate: Cu₃(AsO₄)₂-III, Na₄Cu(AsO₄)₂ und KCu₄(AsO₄)₃

     

The volumes of mixing of aqueous solutions of CdCl2, CuCl2, MnCl2, and ZnCl2 with HCl at varying ionic strength at 25°C

The densities of mixtures of aqueous solutions of hydrochloric acid with solutions of cadmium chloride, copper chloride, manganese chloride, and zinc chloride have been measured at constant ionic strengths of 1.0 and 3.0 mol-kg^–1 at 25°C. The density data were used to determine the volumes of mixing (V _m ). The volume of mixing equations of Pitzer were then fit to the resulting V _m data to obtain the Pitzer parameters _V ^MN and _V ^MNX , which are the pressure derivatives of the free energy equation parameters.     

Cleavage of 1,4-diphenylbuta-1,3-diyne on a ruthenium-cobalt cluster: Synthesis and molecular structure of Co2Ru3(μ4−C2Ph)(μ3−C2Ph)(μ-dppm)(μ-CO)2(CO)9

The reaction between Ru₃(₃-²-PhC₂C=CPh)(-dppm)(CO)₈ and Co₂(CO)₈ afforded dark red Co₂Ru₃(₄-C₂Ph)(₃-C₂Ph)(-dppm)(-CO)₂(CO)₉, shown by an X-ray structure determination to contain a strongly twisted Co₂Ru₃ bow-tie cluster (central Co), to which two PhC₂ units derived from cleavage of the original diyne are attached. One a these is strongly interacting with four metal atoms, the other being attached in the familiar ¹,2²-mode. The dppm ligand remains bridging two of the Ru atoms.