Complexation with diol host compounds. Part 1. Structures of the 1:2 molecular complexes oftrans-9, 10-dihydroxy-9,10-diphenyl-9,10-dihydroanthracene with acetophenone and with 3-methylcyclopentanone

The structures of the 1:2 molecular complexes of trans -9,10-dihydroxy-9,10-diphenyl-9,10-dihydroanthracene with acetophenone (1), (C₂₆H₂₀O₂·2 C₈H₈O) and with 3-methylcyclopentanone (2), (C₂₆H₂₀O₂·2C₆H₁₀O) have been determined by X-ray crystallography. The crystal data are as follows: Compound (1):P ,a =8.979(5) Å,b =9.316(3) Å,c = 11.12(1) Å, =94.40(6)°, = 106.53(6)°, = 109.92(5)°,V = 822.94 ų,Z = 1,R = 0.097 for 2549 unique reflections. Compound (2):P ,a = 8.958(7) Å,b =9.815(4) Å,c = 9.807(4) Å, = 96.88(3)°, = 109.21(8)°, = 103.33(7)°,V = 774.10 ų,Z = 1,R = 0.059 for 2494 unique reflections. The intermolecular arrangements in both structures are characterised by host-to-guest hydrogen bonding interactions. The thermal properties of compound (2) have been characterised by DTA and TGA thermograms.     

IR-spectroscopic studies of strength and concentration of acid centers on V2O5/Al2O3 catalysts

The strength of protonic sites and the concentration of acid centers in V₂O₅/Al₂O₃ catalysts have been estimated according to pyridine and ammonium adsorption.

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V₂O₅/Al₂O₃.

     

Quantitative parameters by thermoanalytical methods

The conditions and premises of the kinetic evaluation of thermoanalytical curves on the basis of chemical kinetics are demonstrated, and the limits of their availability are pointed out. For reactions with an unclear structural and chemical course, some appropriate definitions of terms are proposed.The possibilities of the use of the inflection points of the reaction rate versus time curve are presented. New methods of determination of kinetic parameters are described, including the ratio of the degrees of reactionx, the ratio of the reaction ratesx and the ratio of the tangent slopesx at these points.

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Zusammenfassung Bedingungen und Voraussetzungen der kinetischen Auswertung thermoanalytischer Meßkurven auf der Basis der chemischen Kinetik werden dargestellt, gleichzeitig wird auf die Grenzen ihrer Gültigkeit hingewiesen. Für Reaktionen mit unklarem chemischem oder strukturellem Ablauf werden geeignete neue Bezeichnungen definiert.Die Möglichkeit zur Verwendung der Wendepunkte der Kurve Reaktionsgeschwindigkeit gegen Zeit vorgestellt. Neue Methoden werden beschrieben, die zur Bestimmung kinetischer Parameter das Verhältnis der Umsätzex ₁ x ₂, das Verhältnis der Reaktionsgeschwindigkeitenx ₁/x ₂, und das Verhältnis der Tangentensteigungenx ₁/x ₂ an den Wendepunkten verwenden.

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. . . — . , (x), () () .

     

Thermal properties of thio-and selenocyanatocopper(II) complexes with bipyridine and phenanthroline

The paper deals with the thermal properties of complex compounds of the general formula CuL₂(NCX)₂ (whereL=bipy or phen,X=S or Se). The phenanthroline complexes exhibit a higher thermal stability than those with bipyridine. For the latter complexes thermal decomposition begins with the release of bipyridine molecules, while for the phenanthroline complexes redox reactions of pseudohalogenide ligands with Cu(II) take place. The redox reactions start at a lower temperature for the selenocyanate complexes than for the thiocyanate complexes.

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Zusammenfassung Vorliegende Arbeit behandelt die thermischen Eigenschaften von Komplexverbindungen der allgemeinen Formel CuL₂(NCX)₂ (mitL=Bipyridin oder Phenanthrolin undX=S oder Se). Die Phenanthrolinkomplexe zeigen eine grössere thermische Stabilität als die Bipyridinkomplexe. Die thermiscne Zersetzung letzterer beginnt mit der Abgabe von Bipyridinmolekülen, während bei den Phenanthrolinkomplexen Redoxreaktionen von Pseudohalogenidliganden·mit Cu(II) stattfinden. Diese Redoxreaktionen beginnen bei den Selenozyanatkomplexen bei niedrigeren Temperaturen als bei den Thiozyanatkomplexen.

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CuL₂(NCX)₂, L= , X= . . , — . - , .

     

Medium effects on the reactions of coordination complexes: Base hydrolysisof(αβS)(p-hydroxybenzoato)(tetraethylenepentamine) cobalt(III) in iso-propanol–water,tert-butanol–water and dimethyl sulfoxide–water media

The base hydrolysis of (S)(p-hydroxybenzoato)-(tetraethylenepentamine)cobalt(III) has been investigated in aqueous–organic solvent media using i-PrOH, t-BuOH and dimethyl sulfoxide (DMSO) as cosolvents at 20.0 T (°C) 40.0 (I=0.02 mol dm ^-3) with 80% (v/v) of cosolvents. Only the base-catalysed path (k_obs=k_OH[OH^-]) is observed. The relative second order rate constant k _OH ^os /k _OH ^ow at I=0 increases nonlinearly with increasing mol fraction (x_O.S.) of the cosolvents, the rate acceleration in alcoholic cosolvents being greater than in DMSO. The destabilization of ^-OH in mixed solvent media alone does not explain the observed rate acceleration. The solvent composition dependence, log k _OH ^os = log k _OH ^ow + a_ix _os ⁱ [i=1,2,k _OH ⁰ denotes k_OH at I=0 in mixed solvent(s) and water (w)] indicates specific solute–solvent interactions. The values of the relative transfer free-energy data [_TG(t.s.) - _TG^o (i.s.)](sw)(25 °C)(G), where t.s. and i.s. denote the transition state and initial state of the substrates respectively, are positive for all substrates at all compositions, indicating a greater destabilizing effect of the mixed solvent on the transition state than on the initial state. The G values also correlate with G^E(G = ax_O.S. + cG^E) for all solvents, supporting the fact that solvent structural effects mediate the rates and energetics of the reaction. However, the solvent effects on the solvation components of H and S are mutually compensating, thus indicating that there is no change in the mechanism.     

Effect of magnetic order on the conductivity in Co-Zn ferrites

A series of samples in the system Co_1–xZn_xFe₂O₄ (x=0.3, 0.4, 0.6, 0.8 and 1) were prepared by the usual ceramic technique. The D. C. electrical resistivity and thermoelectric power were measured in the temperature range from room temperature up to about 600 K. Transition from the ferrimagnetic region to the paramagnetic region is accompanied by an increase in the activation energy by an amountE, which varies in the range 0.052–0.090 eV. The large values ofE obtained may be due to the fairly strong B-B exchange interaction in Co-Zn ferrites.

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Zusammenfassung Mittels üblicher Keramiktechniken wurden Proben des Systemes Co₁–xZn_xFe₂O₄ unterschiedlicher Zusammensetzung (x=0,3, 0,4, 0,6, 0,8, 1,0) dargestellt. Im Temperaturbereich Raumtemperatur-600 K wurde der elektrische Widerstand gegenüber Gleichstrom sowie die Thermospannung dieser Proben ermittelt. Der Übergang von der ferrimagnetischen zur paramagnetischen Region wird von einem Anwachsen der Aktivierungsenergie um den BetragE=0,052–0,090 eV begleitet. Den so erhaltenen grossen E-Werten liegen wahrscheinlich die ziemlich starken B-B Austausch Wechselwirkungen in Co-Zn Ferriten zu Grunde.

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_1–xZn_xFe₂₄ =0,3;0,4;0,6;0,8 1, 600 . E, 0,052–0,090 . E - - .

     

SIMS studies of water vapor adsorption on polycrystalline rhodium

Studies of water vapor adsorption on polycrystalline Rh at T>315 K and P=(2–4)×10^–2 Pa indicate that water is adsorbed dissociatively to O_ads and O_ads through a molecularly adsorbed species. Desorption activation energy is 46 and 69 kJ/mol for molecular and dissociative species, respectively.

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Rh (2–4)·10^–2 . , O OH - . 46 /, -69 /.

     

Activation of magnesia by hydrogen spillover

Magnesia aerogel activated by hydrogen spillover at 430 °C or at 200 °C becomes a catalyst for the hydrogenation of ethylene. This catalytic activity, observed already at 50 °C, is further enhanced by a treatment in oxygen at 430 °C.

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, 430 200°C, . 50°C 430°C.

     

Reaction of ammonium sulphate with aluminium oxide

The reaction between ammonium sulphate with aluminium oxide was studied. It was confirmed by X-ray diffraction and chemical analysis that three intermediate reaction products, (NH₄)₃Al(SO₄)₃, NH₄Al(SO₄)₂ and Al₂(SO₄)₃, are formed. The thermal decompositions of these three compounds were carried out. It has been shown that the same rate law is valid for them. The activation energies for (NH₄)₃Al(SO₄)₃, NH₄Al(SO₄)₂ and Al₂(SO₄)₃ are 95.9, 177.9 and 291.0 kj/mol, respectively.

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Zusammenfassung Die Reaktion von Ammoniumsulfat mit Aluminiumoxid wurde untersucht. Durch Röntgendiffraktion und chemische Analyse wurde bestätigt, daß drei Zwischenprodukte (NH₄)₃Al(SO₄)₃, NH₄Al(SO₄)₂ und Al₂(SO₄)₃ gebildet werden. Die thermische Zersetzung der drei Verbindungen wurde durchgeführt. Es wurde gezeigt, daß für alle drei dasselbe Geschwindigkeitsgesetz Gültigkeit hat. Die Aktivierungsenergien für (NH₄)₃Al(SO₄)₃, NH₄Al(SO₄)₂ und Al₂(SO₄)₃ sind 95.9, 177.9 und 291.0 kJ/Mol.

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. - : (NH₄)₃Al(SO₄)₃, NH₄Al(SO₄)₂ Al₂(SO₄)₃. , , . (NH₄)₃Al(SO₄)₃, NH₄Al(SO₄)₂ Al₂(SO₄)₃, , 95.9; 177.9 291.0 . ^–1.

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The authors are grateful to Dr. H. Osada and Mr. H. Nakamura, Department of Environmental Engineering, Kyushu Institute of Technology, for their helpful discussions.     

Thermogravimetry of copper and copper oxides (Cu2O-CuO)

The thermogravimetry of mixtures of metallic copper and copper oxides was studied. The experiments were performed by heating the samples in air to 700–800° to transform all the components to copper(II) oxide, and continuing the heating in nitrogen to 1050–1100° when the dissociation of copper(II) oxide to copper(I) oxide is complete. The identification of the components and their quantitative determination were carried out by determining the shape, size, and ratio of the segments of the curves obtained during the heating. The method can be used for quantitative analysis of mixtures of copper and/or copper oxides.

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Zusammenfassung Gemische von metallischem Kupfer und Kupferoxiden wurden thermogravimetrisch untersucht. Zur Überführung aller Komponenten in Kupfer(II)-oxid erhitzte man sie in Luft auf 700–800°, um daraufhin bis zur vollständigen Dissoziation des Kupfer-(II)-oxids zu Kupfer(I)-oxid unter Stickstoff die Temperatur bis auf 1050–1100° zu steigern. Die Identifizierung der Komponenten und ihre quantitative Bestimmung erfolgten durch die Form, Größe und die Verhältnisse der verschiedenen Abschnitte der erhaltenen Kurven. Diese Methode ist zur quantitativen Bestimmung von Gemischen aus Kupfer und Kupferoxid sowie von Kupferoxiden geeignet.

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Résumé Étude thermogravimétrique de mélanges du cuivre métallique et d'oxydes de cuivre. Les échantillons sont d'abord chauffés dans l'air jusqu'à 700–800° jusqu'à ce que tous les constituants soient transformés en oxyde de cuivre(II); le chauffage est ensuite poursuivi dans l'azote jusqu'à 1010–1100°, où la dissociation de l'oxyde de cuivre(II) en oxyde de cuivre(I) est complète. Les constituants ont été identifiés et dosés en utilisant la forme, la dimension et les proportions des différentes parties des courbes pendant le chauffage. La méthode peut être utilisée pour l'analyse quantitative de mélanges de cuivre et ou d'oxydes de cuivre.

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. 700–800: ( (), 1050–1100° [ () (I)]. , , . / .

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The author wishes to acknowledge the financial assistance provided by the Technion — Israel Institute of Technology.The author wishes also to thank Dr. R. F. Tylecote (University of Newcastle Upon Tyne, England) for very helpful comments and useful discussions of this investigation and to Mrs. N. Leder for chemical analyses.     

Studies of Cu?Ni supported catalysts for enantioselective hydrogenation

The effect of support content and composition of supported metal phase on the crystallite size, phase composition and catalytic properties of supported Ni and Cu–Ni catalysts has been investigated. It has been established that with increasing metal content, crystallite sizes and enantioselectivity increase. Copper added to Ni catalysts decreases metal phase dispersity and enantioselectivity.

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, , - . , . є .

     

Structural studies of nickel-based Raney catalysts

Electron microscopy and Mössbauer spectroscopy studies of nickel-based Raney catalysts have revealed that the catalysts are formed through the successive aggregation of their structural elements. Catalyst particles are covered by a thin layer of nickel oxide.

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. , . .

     

m-Xylene conversion over dealuminated Y zeolites studied by the pulse method

m-Xylene conversion was studied over dealuminated Y type zeolites in hydrogen forms, SiO₂ to Al₂O₃ ratios were varied from 4.86 to 12.95.

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- . SiO₂/Al₂O₃ 4,86 12,95.

     

Synthesis of some 5′-O-amino acid derivatives of uridine as potential inhibitors ofUDP-glucuronosyltransferase

Summary In an attempt to develop potential inhibitors ofUDP-glucuronosyltransferase, some 5-O-amino acid derivatives of uridine were synthesized. N-protectedL-amino acids were coupled at the 5-O-position of 2,3-O-isopropylideneuridine by esterification employing the method of symmetrical anhydrides in presence of 4-dimethylaminopyridine, 5-O-(N-benzyloxycarbonyl-O-tert.butyl-L-threonl)-23-O-isopropylideneuridine (1), 5-O-(N-tert.butyloxycarbonyl-O-benzyl-L-seryl)-2,3-O-isopropylideneuridine and (2), 5-O-(N-tert.butyloxycarbonyl-L-valyl)-2,3-O-isopropylideneuridine (3), and 5-O-(N-tert.butyloxycarbonyl-L-valyl)-2,3-O-isopropylideneuridine (4) were obtained in good yield after column chromatography on silica gel. The treatment of2 withTFA/CH₂Cl₂ (6:1) at room temperature for 30 min led to a selective removal of theBoc group without deblocking of the 2,3-O-isopropylidene group of uridine. Treatment of2 withTFA/H₂O (5:1) at room temperature for 1 h, however, released bothBoc and 2,3-isopropylidene groups. TheZ group of1 was deprotected by catalytic hydrogenolysis over 10% Pd/C/ammonium formate.

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Synthese von 5-O-Aminosäurederivaten des Uridins als potentielle Inhibitoren derUDP-Glukuronosyl-Transferase

Zusammenfassung In einem Versuch, potentielle Inhibitoren derUDP-Glukuronosyl-Transferase zu entwickeln, wurden einige 5-O-Aminosäurederivate des Uridins synthetisiert. N-GeschützteL-Aminosäuren wurden durch Veresterung mit der 5-O-Position des 2,3-isopropylidenuridins gekuppelt (Methode der symmetrischen Anhydride in der Gegenwart von 5-Dimethylaminopyridin). Solcherweise wurden 5-O-(N-Benzyloxycarbonyl-O-tert.butyl-L-threonly)-2,3-O-isopropylidenuridin (1), 5-O-(N-tert.Butyloxycarbonyl-O-benzyl-L-seryl)-2,3-O-isopropylidenuridin (2), 5-O-(N-tert.Butyloxycarbonyl-L-leucyl)-2,3-O-isopropylidenuridin (3) und 5-O-(N-tert.Butyloxycarbonyl-L-valyl)-2,3-O-isopropylidenuridine (4) nach Säulenchromatographie (Kieselgel) in guter Ausbeute hergestellt. Die Behandlung von2 mitTFA/CH₂Cl₂ (6:1) bei Zimmertemperatur (30 min) führte zu einer selektiven Abspaltung derBoc-Gruppe ohne Deblockierung der 2,3-O-Isopropylidengruppe des Uridins. Eine Behandlung von2 mitTFA/H₂O (5:1) bei Zimmertemperatur für 1 Stunde führte hingegen zur Abspaltung sowohl derBoc als auch der 2,3-O-Isopropylidengruppe. DieZ-Gruppe von1 wurde durch katalytische Hydrogenolyse auf 10% Pd/C/Ammoniumformiat abgespalten.

     

Komplexbildung im System Ni2+—o-Methylbenzamidoxim

Zusammenfassung Die Komplexe des Ni²⁺ mit o-Methylbenzamidoxim wurden in neutraler und in alkalischer Lösung spektrophotometrisch untersucht. Die Bildungskonstanten sindK ₁=40 für 11 undK ₂=1,7·10² für 12 in neutraler Lösung und ₁ = =(3,92 ±0,2) · 10⁴für 11 und lgK = lg ₁ + lg ₂ = 3,45 ± ±0,15 für 12 bei 25° und =1 in alkalischer Lösung.

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Complex formation in the systemeNi ²⁺—o-methylbenzamide oxime

The complexes of Ni²⁺ with o-methylbenzamide oxime were investigated spectrophotometrically in neutral as well as in alkaline solution. The formation constants areK ₁=40 for 11 andK ₂=1.7·10² for 12 in the neutral solution and ₁ = =(3.92 ±0.2) · 10⁴ for 11 and lgK = lg ₁ + lg ₂ = 3.45 ± ±0.15 for 12 at 25° and =1 for the alkaline solution. *** DIRECT SUPPORT *** A3615139 00007

     

Analysis of thermal desorption spectra of oxygen desorbed from rhodium

Thermal desorption spectra of oxygen desorbed from rhodium have been analyzed in terms of models accounting for the effect of lateral interactions between adsorbed particles and of their diffusion into the bulk of metal on the desorption kinetics of O₂. Complex configuration of these spectra is ascribed to the processes of formation/decomposition of surface Rh oxides and the diffusion of particles into the near-surface layers of metal and back to the surface.

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- , O₂ . - O₂ Rh - .

     

The twisted skeleton of 1,9-diaminononane incatena-[catena-,μ-(1,9-diaminononane)cadmium(II) tetra-μ -cyanonickelate(II)]-o-xylene(2/1)

The Hofmann-danon-typeo-xylene clathrate Cd[NH₂(CH₂)₉NH₂]Ni(CN)₄·0.5(CH₃)₂C₆H₄, crystallizes in the triclinic space groupP witha = 15.118(3),b = 14.048(4),c = 7.325(1) Å, = 91.50(2), = 131.66(3), and = 107.50(2)°,V = 1051(1) ų andZ = 2. The structure, refined toR = 0.047 using 2851 reflections, reveals a three-dimensional host framework built of the layers of a two-dimensionalcatena-[cadmium tetra--cyanonickelate(Il)] network and of the ambidentate 1,9-diaminononane (danon) bridging the Cd atoms in adjacent networks. The guesto-xylene molecule is accommodated in the cavity formed in the interlayer space similar to that in the Hofmann-daotn-type. The skeleton of the danon in the Cd-NC₉N-Cd linkage takes a (gauche)₂(trans)₈ conformation twisted at the (gauche)₂ part in contrast with the all-trans conformation of 1,8-diaminononane in the Hofmann-daotn-type clathrate. The twisted (gauche)₂ part of the danon skeleton occupies the interlayer space to such an extent that void space available for the guest o-xylene molecule decreases to half that in the Hofmann-daotn-type clathrate Cd[NH₂(CH₂)₈NH₂]Ni(CN)₄·G.The Crystal structures of ,-Diaminoalkanecadmium(II)Tetracyanonickelate(II) - Aromatic Molecule Inclusion Compounds. VI.     

Steroid compounds of marine sponges. VII. Preparation of derivatives of sokotrasterol and halistanol sulfates and structure-activity interrelationships among these compounds

Five new sulfated derivatives of sokotrasterol and halistanol have been obtained: 24-nor-5-cholane-2,3,6,23-tetraol 2,3,6-tri(sodium sulfate); 24-nor-5-cholane-2,3,6,23-tetraol 2,3,6-tri(sodium sulfate) 23-palmitate; 24,25-dimethyl-5-cholestane-2,3,6-triol 3-(sodium sulfate); 24,25-dimethyl-5-cholestane-2,3,6-triol 6-(sodium sulfate); and 24,25-dimethyl-5-cholestane-2,3,6-triol 2,6-di(sodium sulfate). The inhibiting and membranolytic properties of the polysulfated steroids from sponges and their derivatives have been studied. It has been shown that physiological activity in this series of compounds depends on biphilicity.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 441–445, July–August, 1986.