Über Verbindungen mit Urotropin-Struktur, 37. Mitt.: Eine neue Methode zur Herstellung von Hydroxy-ketonen und Diketonen sowie ihre Anwendung auf die Synthese des 2,4-Dioxa-adamantan-Ringsystems

Zusammenfassung Es wird eine neue Methode zur Herstellung von Hydroxyketonen und Diketonen beschrieben, die im ersten Schritt der Reaktionsfolge die Umsetzung von Hydroxycarbonsäureestern mit Phenylsulfonalkylmagnesiumbromid zu -Sulfonylketonen erfordert. Diese werden dann im zweiten Schritt mit Al-Amalgam zu den Hydroxyketonen oder den Halbketalen der Diketone entschwefelt. Mit Hilfe dieser Reaktionsfolge gelang auch, ausgehend von 3,5-Dihydroxy-phenylessigsäureester, die Synthese des bisher noch unbekannten Ringsystems des 2,4-Dioxa-adamantans.Herrn Prof. Dr. habil.Friedrich Asinger zum 60. Geburtstag in freundschaftlicher Verbundenheit zugeeignet36. Mitt.:H. Stetter, J. Gärtner undP. Tacke, Chem. Ber.99, 1435 (1966).     

Bestimmung des Gleichgewichts der salpetrigen Säure mit Nitritacidium-Ion auf chemischem Wege

Zusammenfassung Die Struktur des Nitritacidium-Ions¹ kann nach einer Interpretation vonSeel mit der Mesomerie zwischen zwei Grenzzuständen A und B (s. S. 428) erklärt werden. Es ist anzunehmen, daß sich bei einer Verminderung der Aktivität des Wassers der Resonanzzustand des Ions in Richtung von A nach B verschiebt. In sehr schwach perchlorsaurer, wäßriger Lösung läßt sich die Gleichgewichtskonstante der Bildung des Nitritacidium-Ions aus salpetriger Säure und Wasserstoffion aus kinetischen Daten vonHermann Schmid näherungsweise berechnen. In sehr stark perchlorsaurer, wäßriger Lösung läßt sich diese Gleichgewichtskonstante unter Verwendung der SäurefunktionJ ₀ aus Gleichgewichtsmessungen des Salpetrigsäurezerfalles ermitteln. (Der gefundene Wert stimmt mit den vonSeel und vonDeno, Berkheimer, Evans undPeterson aus optischen Untersuchungen erhaltenen Werten und mit dem kürzlich vonGerhard Schmid undU. Neumann mit Hilfe der NO/NO⁺-Elektrode gemessenen Wert größenordnungsmäßig überein.) Der vonChallis undRidd gefundene Mediumeffekt bei der Diazotierung aromatischer Amine in perchlorsaurer, wäßriger Lösung kann durch die oben erwähnte Verschiebung in der Resonanzstruktur des Nitritacidium-Ions erklärt werden.     

The Reagent‐depending Nitration of 1,3‐Dihydroxyacetone Dimer

Two highly energetic nitric acid esters were synthesized from the dimer of dihydroxyacetone. 1,3‐Dinitratoacetone ( 1 ) and its dimer 2,5‐bis(nitratomethyl‐2,5‐nitrato)‐1,4‐dioxane ( 2 ) were characterized by single‐crystal X‐ray diffraction, vibrational spectroscopy (IR and Raman), multinuclear NMR spectroscopy, and elemental analysis. The thermal behavior was investigated with DTA measurements. Although showing the same atomic stoichiometry, dimer 2 shows significantly higher sensitivities measured by BAM methods (drophammer and friction tester). Due to the high oxygen content of 62.2 %, 1 and 2 were evaluated as potential high energy dense oxidizers.     

(Meta)stabiles CaC2

(Meta)stable CaC₂ One out of four modifications of CaC₂ is the so‐called metastable Calcium Carbide, CaC₂‐III, which was synthesized as pure material. It forms by heating monoclinic CaC₂‐II (C2/c) above 150 °C and remains stable after cooling down to room temperature. The structure was refined from X‐ray powder patterns (C2/m, Z = 4, a = 722.6(1) pm, b = 385.26(7) pm, c = 737.6(1) pm, β = 107.345(2)°). After grinding CaC₂‐III transforms back into CaC₂‐II. Heating CaC₂‐III induces a reversible phase transition into the cubic modification (CaC₂‐IV) at 460 °C. Differences between the three different structures of CaC₂ I–III, being stable at ambient conditions are also shown by ¹³C‐MAS‐NMR measurements, especially the presence of two distinct types of carbon atoms in the structure of the title compound.     

Mehrfachbindungen zwischen Hauptgruppenelementen und Übergangsmetallen : XLIV. Synthesen von Hydrogensulfido- und Hydrogenselenido-Komplexen der Metalle Chrom, Molybdän und Wolfram

Hydrogenchalcogenido complexes of general composition (η⁵-C₅R₅)(CO)₃M(EH) (R = H, CH₃; M = Cr, Mo, W; E = S, Se) can be obtained by three different routes, sometimes in quite good yields. Thus, the sulfur and selenium derivatives can be synthesized by insertion of the respective elements into the metal-hydrogen bonds of the precursor compounds (η⁵-C₅R₅)(CO)₃MH. This species also reacts with potassium selenocyanate to yield the hydrogenselenido derivatives (η⁵-C₅R₅)(CO)₃M(SeH) which can also be obtained by treatment of the methyl complexes (η⁵-C₅R₅)(CO)₃M(CH₃ (M = Mo, W) with HBF₄ and Li[SeH]. The corresponding hydrogentellurido compounds are probably formed by these preparative methods but appear to be quickly converted into either the dinuclear tellurium bridge products (μ-Te)[(η⁵-C₅R₅)(CO)₃M]₂ (M = Mo) or into the hydrido complexes (η⁵-C₅R₅)(CO)₃MH (M= Mo, W) by release of elemental tellurium.     

Influence of calcium-induced aggregation on the sensitivity of aminobis(methylenephosphonate)-containing potential MRI contrast agents

A novel class of 1,4,7,10-tetraazacyclododecane-1,4,7-tris(methylenecarboxylic) acid (DO3A)-based lanthanide complexes with relaxometric response to Ca(2+) was synthesized, and their physicochemical properties were investigated. Four macrocyclic ligands containing an alkyl-aminobis(methylenephosphonate) side chain for Ca(2+)-chelation have been studied (alkyl is propyl, butyl, pentyl, and hexyl for L(1), L(2), L(3), and L(4), respectively). Upon addition of Ca(2+), the r(1) relaxivity of their Gd(3+) complexes decreased up to 61% of the initial value for the best compounds GdL(3) and GdL(4). The relaxivity of the complexes was concentration dependent (it decreases with increasing concentration). Diffusion NMR studies on the Y(3+) analogues evidenced the formation of agglomerates at higher concentrations; the aggregation becomes even more important in the presence of Ca(2+). (31)P NMR experiments on EuL(1) and EuL(4) indicated the coordination of a phosphonate to the Ln(3+) for the ligand with a propyl chain, while phosphonate coordination was not observed for the analogue bearing a hexyl linker. Potentiometric titrations yielded protonation constants of the Gd(3+) complexes. log K(H1) values for all complexes lie between 6.12 and 7.11 whereas log K(H2) values are between 4.61 and 5.87. Luminescence emission spectra recorded on the Eu(3+) complexes confirmed the coordination of a phosphonate group to the Ln(3+) center in EuL(1). Luminescence lifetime measurements showed that Ca-induced agglomeration reduces the hydration number which is the main cause for the change in r(1). Variable temperature (17)O NMR experiments evidenced high water exchange rates on GdL(1), GdL(2), and GdL(3) comparable to that of the aqua ion.     

Intramolecular Alkylation of Aromatic Compounds XXXVI [1]. Stereoselective Synthesis of C/D-cis-Configured Ergolines

Summary.  The stereoselective synthesis of cis-ergoline is presented. Starting from rac-N-benzoyl tryptophan methyl ester, the key compound indolinylmethylpyridin-3-one was prepared via a seven-step reaction in good yield. Since its cyclization to the desired ergolinone failed, the key compound was reduced to yield the two diastereomeric pyridin-3-ols; only one of them cyclized in trifluoromethanesulfonic acid, affording cis-ergoline. Catalytic hydrogenation of the latter gave N,N′-dimethyldihydroergoline, the X-ray crystallography of which revealed both the correct structure and identical relative configurations at C-5a and C-6a (SS or RR). Hydroboration and subsequent perruthenate oxidation of the Δ⁹-ergoline provided access to the regioisomeric ergolinols and ergolinones. Received December 27, 2001. Accepted January 15, 2002     

Preparative high-performance liquid chromatography of peptides on a new reversed-phase packing material, Kromasil C18

Preparative reversed-phase high-performance liquid chromatography has found wide use in the production of peptides for pharmaceutical formulations. Purity of the substance and overall economy of the chromatographic system are the most important criterias. In this sense optimized, silica particles and production process with capability to separately control parameters important to chromatography, are essential to high-performance chromatography. Kromasil C18 packing material was tested and evaluated in respect of its selectivity, flow and pressure properties, resolution, load capacity, recovery, adsorption effects, mechanical strength and chemical degradation.