Diels-Alder-Reaktionen von Vinylindolen mit Arin und 1,4-Benzochinonen: Neue potentielle DNA-Interkalatoren

Summary Diels-Alder reactions of 2- and 3-vinylindoles with aryne, 1,4-benzo- and 1,4-naphtho-quinone lead to new six-ring annellated carbazoles. Molecular modeling studies predict that the compounds with coplanar framework are able to intercalate with the B-DNA.

     

New evidence on the structure of potassium salts of 12-tungstophosphoric acid, KxH3-xPW12O40

Physicochemical properties and compositions of KxH(3-x)PW12O40 salts, where 2 < or = x < or = 3, have been investigated. It has been found that freshly prepared K2HPW12O40 salt (drying at 313 K) contains particles of heteropolyacid and particles of the neutral potassium salt, the sample being in 78.6% amorphous. On aging at room temperature, the heteropolyacid spreads to form a surface layer covering the neutral potassium salt particles K3PW12O40. Heat treatment of KxH(3-x)PW12O40 salts, where 2 < or = x < 3, from 313 K to higher temperatures induces the transformation of the heteropolyacid-covering K(3) core into a well-dispersed, amorphous surface layer. On further heating of the acidic potassium salts, the surface layer decomposes between 855 and 915 K with the formation of a PW8O26-type bronze as a new phase, the K3PW12O40 salt remaining unchanged. The latter starts to decompose at 1093 K, and in the case of all samples, the process is completed at about 1183 K. Rietveld structure refinement, XPS, and 31P NMR measurements of acidic potassium salts indicate that the core of these salts is always formed by the K3PW12O40 salt, which is covered by a heteropolyacid. Comparison of lattice parameters of the K3 salt and HPW leads to the conclusion that the layer is composed of partially or completely dehydrated heteropolyacid molecules. The coverage of the core by HPW in the K2 sample was estimated to be equal to one monolayer.     

The polymorphic transformations of cobalt molybdate

Polymorphic transformations of CoMoO₄ were studied by means of high temperature X-ray measurements within the temperature range 25–1200°C. On heating phase a obtained from low temperature modification b a new modification a′ was discovered. Phase a obtained by thermal decomposition of solvated α-CoMoO₄ shows different behaviour. At 700–930°C depending on the conditions of preparation it transforms irreversibly into still another modification a″. On cooling, a mixture of phases a + a″ is obtained, the presence of a″ being responsible for the explosionwise transition into b, observed around the room temperature.     

IR-spectroscopic studies of the interaction of propylene and acrolein with a CoMoO4 catalyst

IR spectra of propylene and acrolein adsorbed at different temperatures on CoMoO₄ supported on MgO were recorded. Four different surface species were found: a -complex, an oxygen bonded carbonyl complex, acrylic acid and a carboxylate type complex. The mechanism of their transoformation is discussed.

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- CoMoO₄ MgO. , 4 : -, , , . .

     

Influence of the oxide matrix on the electronic state of vanadium ions

ESCA spectra of V₂O₅, V₂O₅/TiO₂ and V₂O₅ dissolved in TiO₂ were recorded after oxidation and reduction. V⁴⁺ ions have the same effective charge in reduced V₂O₅ and in TiO₂, whereas the effective charge of V⁵⁺ ions in TiO₂ is higher than in V₂O₅, indicating enhanced electron acceptor properties.

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V₂O₅, V₂O₅ TiO₂ V₂O₅ TiO₂ . , V⁺⁴ V₂O₅ TiO₂ V⁺⁵ TiO₂ V₂O₅, .

     

Efficient synthesis of 4-aminoquinazoline and thieno[3,2-d]pyrimidin-4-ylamine derivatives by microwave irradiation

[reaction: see text] A simple, efficient, and high-yielding synthesis of quinazolin-4-ylamine and thieno[3,2-d]pyrimidin-4-ylamine derivatives is reported under microwave irradiation conditions. Reaction conditions including temperature, solvent, and reaction time have been studied. An efficient parallel workup procedure was developed to generate a small library (23 compounds) in a short time period.     

Oxidation of naphthalene on olefin oxidation catalysts

Oxidation of naphthalene on Co–Mo–O, NiMoO₄ and Mg–Mo–O catalysts gives phthalic anhydride, its maximal yield being about 40% on nickel molybdate. On bismuth molybdates and the Sn–Sb–O system, naphthalene is mainly oxidized to carbon oxides.

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Co–Mo–O, NiMoO₄ Mg–Mo–O , ( 40%) . Sn–Sb–O .

     

Electron spectroscopic studies of the reduction of WO3

Five different doublets corresponding to W 4f electrons were observed in the course of reduction of WO₃. On contact of WO₃ with hydrogen, W⁵⁺ ions are formed. Reduction results at first in formation of isolated W⁴⁺ ions. Clusters of edge-sharing octahedra on shear planes are then formed, in which pairing of W⁴⁺ ions occurs due to metal-metal bonding, corresponding to an apparent 2+ oxidation state.