Zur Reaktion von Hydrazinen mit Fluorsilanen und lithiierten Aminen

Lithium salts of hydrazines react with fluorosilanes under formation of fluorosilylhydrazines and LiF. Five membered rings are obtained in the reaction of bis(fluorosilyl)-hydrazines with lithiated amines. The mass,¹H-and¹⁹F-nmr spectra of the compounds are reported.

     

Neue Synthesemethoden 2 Milde Einphasenoxidation von Aldehyden zu Carbonsäuren Kurze Mitteilung

The mild oxidation of aldehydes to carboxylic acids with benzyltriethylammoniumpermanganate in organic solvents at roomtemperature is presented.

     

Magnetische Eigenschaften von Hf2Fe und Hf2FeH x

The weakly temperature dependent paramagnetic compound Hf₂Fe becomes ferromagnetic by hydrogen absorption, theCurie-temperature of the resulting hydrides depends on the hydrogen content.

     

Einige neue Thiaspirane

The synthesis of fifteen new (constitutionally nonsymmetrical) dithiaspirans having both sulfur atoms in the 7-membered ring is described. Some aspects of the conformation of the compounds are studied using¹H nmr. Conformational transmission is observed in all cases.

     

Die spontane Etherbrückenöffnung an 7-Oxo-Morphinderivaten

The morphine derivatives1, 4, 7 and10 are potential precursors of 7-oxo-morphine derivatives. Attempts are described to obtain the unknown compounds5, 8, 11 leading to the salutaridine derivatives6, 9 and12. Mechanism and principles are discussed and a new empiric rule is formulated.

     

Protonen-Spin-Gitter-Relaxation und interne Beweglichkeit von Molekülen

Relaxation rates can be used as assignment tool in NMR-spectroscopy; even conformational changes in the cyclic peptide alkaloid frangulanin (1) can be monitored by proton-relaxation measurements. The results are compared with a force-field calculation of (1).

     

On the phase CrTe3

A new phase CrTe₃ was discovered and its existence was confirmed by differential thermal analysis and X-ray investigations. Symmetry and lattice parameters as well as the temperature of its peritectic decomposition were determined.

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Über die PhaseCrTe ₃

Zusammenfassung Eine neue Phase CrTe₃ wurde entdeckt und ihre Existenz wurde mittels differential-thermoanalytischer und röntgenographischer Untersuchungen sichergestellt. Es wurden Symmetrie und Gitterparameter sowie auch die Temperatur des peritektischen Zerfalls bestimmt.

     

Polarographische Untersuchung der Kinetik der Polymerisation von Methylvinylketon

The homogeneous polymerization of methyl-vinyl ketone in diluted methanol solutions in presence of proton donors is studied using the polarographic method. The effect of the cation of the indifferent electrolyte is investigated as well as the influence of small quantities of H₂O. Suggestions were made about the possible mechanisms of these influences in the general scheme of the process proposed byHolleck et al.

     

Cyclisierung von Oligomeren des Malodinitrils mit Amidinen Synthesen mit Nitrilen, 55. Mitt

Condensation of formamidine-acetate with dimeric malononitrile (1 a) leads to 2,4-diamino-3,5-pyridine-dicarbonitrile (3 a), with acetamidine-HCl the methyl derivative3 b is obtained. Reaction of the codimer of malononitrile and methyl cyanoacetate (1 b) with formamidine yields the aminopyridine3 c, while acetamidine and benzamidine, resp. with1 b react to the 1,4-dihydro-4-pyrimidinylidene-methyl-cyanoacetates4 a-b.

     

Benzothiazolo[3,2-c]-1,3-dioxolo[4,5-g]quinazolines

Zusammenfassung Es wurde eine Reihe von 5,12a-Dihydro-6-alkyl/aryl-6H-benzothiazolo [3,2-c]-1,3-dioxolo[4,5-g]chinazoline, sowohl mitcis-als auchtrans-ständigen Wasserstoffatomen an Kohlenstoff 6 und 12a, synthetisiert. Ebenso wurden auch Verbindungen dieses Systems mit Thiazol an Position 6 hergestellt. Die Strukturen wurden mittels IR- und NMR-spektroskopischen Daten abgesichert.

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Benzothiazolo[3,2-c]-1,3-dioxolo[4,5-g]quinazolines

Some 5,12a-dihydro-6-alkyl/aryl-6H-benzothiazolo[3,2-c]-1,3-dioxolo [4,5-g]quinazolines withcis as well astrans stereochemistry of the hydrogens at carbon 6 and 12a have been synthesised. The synthesis of another series of compounds of the above system with thiazole ring at position 6 has also been accomplished. The structures have been established on the basis of IR and PMR data.

     

29Si-NMR-Untersuchungen an einigen Cyclosilanderivaten

²⁹Si-NMR spectras of some new cyclosilane derivatives were measured. First aspects of the dependence of chemical shift on ring size and kind of substituents are given.

     

Zur Bildung eines Benzo-difurans aus Tetrahydroxy-benzochinon

The reaction of tetrahydroxy-benzoquinone with malononitrile is reinvestigated. Spectroscopic and chemical methods establish the structure of the product formed as 2,6-diamino-4,8-dihydro-4,8-dioxobenzo(1,2-b:4,5-b)difuran (2a). Alkylethers of tetrahydroxy-benzoquinone react with malononitrile to give tetraalkoxytricyanovinyl-phenols (5).

     

Mittlere Schwingungsamplituden von SeF4 und TeF4

Mean amplitudes of vibration of SeF₄ and TeF₄ have been calculated from known spectroscopic data in a wide temperature range. The results are briefly discussed and some comparisons with related species are made.

     

The dual role of cytochrome c2 in the facultative phototrophic bacteriumRhodopseudomonas capsulata

Succinate oxidation is stimulated by addition of cytochrome c₂ in cytochrome c₂-deficient spheroplasts from the M6-mutant and from the wild type strain ofRhodopseudomonas capsulata. Inhibition of the alternative oxidase in the wild type by CO facilitates this observation. The finding confirms a dual role of cytochrome c₂, in photosynthetic and in respiratory electron transport.

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Die doppelte Rolle von Cytochrome c₂ in Rhodopseudomonas capsulata

Zusammenfassung Die Oxidation von Succinat wird durch Zugabe von Cytochrom c₂ zu Cytochrom c₂-defizienten Sphäroplasten der Mutante M6 und des Wildtyps vonRhodopseudomonas capsulata stimuliert. Die Hemmung der alternativen Oxidase durch CO im Wildtyp erleichtert diese Beobachtung. Der Befund bestätigt die Doppelrolle von Cytochrom c₂ im photosynthetischen und respiratorischen Elektronentransport.

     

Berechnungen des Metathese-Gleichgewichtes zwischen Cyclopentenylverbindungen, 4-Octen und 4,9-Tridecadien-Derivaten

Empirical force field calculations are used to interpret the occurrence of cyclopentenyl compounds in the course of metathesis degradation of partially isomerized modified poly(1-butenylenes).

     

Neue Synthesemethoden, 4. Mitt.: Milde einphasenoxidation von Sulfiden und Sulfoxiden zu Sulfonen

The mild oxidation of sulfides and sulfoxides to sulfones with benzyltriethylammoniumpermanganate in organic solvents is described.

1Scholz, D., in Vorbereitung.     

Extension of theHüttig isotherm on mixed gas adsorption

Hüttig's theory was extended for mixed gas adsorption. The derived equation is the same as the one that has been obtained byGonzalez andHolland for bilayer adsorption.

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Erweiterung der Hüttig-Isotherme für Gasmischungen (Kurze Mitteilung)

Zusammenfassung Die Theorie vonHüttig wurde auf gemischte Gase ausgedehnt. Die dabei abgeleitete Gleichung ist dieselbe wie die vonGonzalez undHolland für Zweischichtadsorption.

     

Eine Eintopfsynthese von 3-Amino-1H-pyrazol-4-carbonitril

Condensation of malodinitrile with trimethoxymethan and aniline affords 3-anilino-2-cyanoacrylonitrile, which on treatment with hydrazine gives the title compound. Aniline can be recovered almost quantitatively.

     

Synthesis of dipyridyl sulfides from pyridyl-pyridinium halides

Reactions of pyridyl-pyridinium halides with thiolpyridines and thiourea were investigated. New dipyridyl sulfides were obtained by this method.

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Synthese von Dipyridil-sulfiden aus Pyridil-pyridinium-halogeniden

Zusammenfassung Reaktionen von Pyridil-pyridinium-halogeniden mit Thiolpyridinen und Thioharnstoff werden untersucht. Auf diesem Weg wurde eine Reihe neuer Dipyridil-sulfide synthesiert.

     

Zur Reaktivität des neuen Codimeren aus Malonitril und Cyanessigester bzw. dimeren Cyanessigester gegenüber Benzilen

Condensation of benzils with 3-amino-2,4-dicyano-crotonic-ester (2a, b) and dimer cyanoacetate (2c, d) resp. leads to 4,5-diaryl-3-pyrroline-2-ylidenecyanoacetates3a-m. It can be shown by¹³C-spectroscopy that in the monosubstituted benzil1c the carbonyl function adjacent to the unsubstituted phenyl reacts with the methylene group of2a orb. With aqueous alkaline the pyrrolines3 rearrange to pyrrolidinones4a-i.¹H-NMR-CIDNP experiments support the assumption of a partial radical character of this rearrangement.