Stereochemie von Metallocenen, 17. Mitt.: Darstellung und optische Rotationsdispersion von optisch aktiven Halogen-methylcymantrenen

Zusammenfassung Die optisch aktiven Methylcymantren-- und--carbonsäuren bekannter Absolutkonfiguration wurden auf dem Weg: COClCON₃NH₂Hal in die entsprechenden Chlor-, Brom- und Jod-methylcymantrene umgewandelt, und dieORD der genannten Verbindungen sowie die Drehungen der Methylcymantrenylisocyanate (dargestellt aus den Aziden) gemessen. In den Halogen-methylcymantrenen liegen optisch aktive Metallocene vor, bei denen der Beitrag zur Drehung nur aus der Atomchiralität stammen kann, während bei den anderen Methylcymantrenderivaten auch die Konformationschiralität einen Beitrag leistet. Entsprechend sind die [M]_D-Werte der Halogen-methylcymantrene proportional den Polarisierbarkeiten von Hal. DieNMR-Daten der neuen Cymantrenderivate werden mitgeteilt und kurz diskutiert.

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The optically active methylcymantrene-- and--carboxylic acids of known absolute configuration were converted into the corresponding chloro, bromo and iodo methylcymantrenesvia their chlorides, azides and amines. TheORD of these cymantrene derivatives as well as the rotations of methylcymantrenyl isocyanates (prepared from the azides) are reported. The halogen methylcymantrenes represent optically active metallocenes, in which the contribution to the optical rotations originates only from atomic chirality, whilst in the case of the other methylcymantrene derivatives the conformational chirality also contributes. Correspondingly, the [M]_D values of the halogen methylcymantrenes are proportional to the polarizibilities of Hal. TheNMR data of the new cymantrene derivatives are reported and briefly discussed.

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Mit 3 Abbildungen

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16. Mitt.:H. Falk undK. Schlögl, Mh. Chem.99, 578 (1968).

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a) 3. Mitt.:Heike Gowal undK. Schlögl, Mh. Chem.99, 267 (1968); b) 2. Mitt.:Heike Gowal undK. Schlögl, Mh. Chem.98, 2302 (1967); c) 1. Mitt.:S. G. Cottis, H. Falk undK. Schlögl, Tetrahedron Letters [London]1965, 2857.     

An investigation of some experimental parameters in atomic fluorescence spectrophotometry

Atomic fluorescence in flames is measured by an adaptation of a commercially available flame spectrophotometer. A study is reported of the effect of background radiation and source scattering on 3 flames, air-propane, air-hydrogen and air-acetylene, and of the effects of variation of fuel gas pressure, zone of measurement in the flame, analysing monochromator slit-width and wavelength of measurement. The air-propane flame appears to offer several advantages. The atomic fluorescence of 10 metals is described; those of Co, Fe and Mn have not been previously reported. Excitation of spectra is achieved by means of an a.c. xenon arc lamp or individual discharge lamps.     

New method for the differentiation of the isomers of aminophenol

Summary Pyridine-2,6-dialdehyde is used as a reagent in a very simple and fast method for differentiating between theo- andp-isomers of aminophenol.

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Zusammenfassung Pyridin-2,6-aldehyd wurde für die einfache und schnelle Unterscheidung zwischen den o- und p-Isomeren des Aminophenols verwendet.

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Résumé On décrit une méthode simple et rapide dans laquelle Pyridine 2–6 aldehyde est employé pour distinguer entre les isomères de l'aminophénol.

     

Towards Reversibility of Ion Transfer Across the Interface between Valinomycin Membranes and Aqueous Electrolyte Solutions

Valinomycin-based potassium-selective membranes doped with potassium tetrakis(4-chlorophenyl)borate (KClTPB) or sodium tetrakis(4-fluorophenyl)borate (NaFTPB) are studied in KCl, NaCl, and CaCl₂ solutions by potentiometric and electrochemical impedance methods. Before contact with KCl, membranes doped with NaFTPB provide Nernstian potentiometric response to Na⁺ ions, which is lost after conditioning the membranes in KCl. The membranes doped with KClTPB even before contact with KCl give no Nernstian response to Na⁺ ions. In CaCl₂ solutions, none of the membranes provide a regular potentiometric response. Despite the difference in potentiometric behavior, the impedance spectra of the membranes are very similar in all solutions regardless of prior conditioning of the membranes. No evidence for a hindrance towards charge transfer processes is observed. The results suggest that the membrane/solution interface is reversible for interfering ions as well as for potassium, and the contamination of solutions with the latter is the sole reason for the lack of Nernstian response in the interfering electrolytes.     

Copolymerization of 1-Vinyl-1,2,4-triazole with 2-Hydroxyethyl Methacrylate

Radical copolymerization of 1-vinyl-1,2,4-triazole with 2-hydroxyethyl methacrylate in dimethylformamide and ethanol, initiated with azobis(isobutyronitrile), was studied. The copolymerization constants of this pair of monomers at low conversions and the microstructure parameters were determined. New highly hydrophilic thinly cross-linked copolymers were prepared from these monomers in the presence of crosslinking agents.     

Studies of carbazole-based polyarylates

A low temperature solution condensation method with pyridine as acceptor-catalytic reagent was applied to the synthesis of polyarylates from carbazole and bisphenol A/phenolphthalein. The polyarylates were classified with respect to their structure, thermal stability, and dielectric behavior.     

Synthesis and spatial structure of the geometrical isomers of 4-substituted 1-tert-butyl-3-methyl-piperidin-4-ols and 4-acyloxy-1-tert-butyl-3-methylpiperidines

In order to study the interrelationship between the structure, reactivity, and spectroscopic characteristics of the stereoisomeric piperidines, starting from 1-tert-butyl-3-methylpiperidin-4-one the synthesis has been performed of the geometric isomers of some 4-substituted 1-tert-butyl-3-methylpiperidin-4-ols and 4-acyloxy-1-tert-butyl-3-methylpiperidines. The spatial structures of the compounds obtained have been determined by IR and PMR spectroscopy.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1056–1061, August, 1973.     

Die Molekül- und Kristallstruktur von Di-μ-sulfato-μ-hydroxo- bis[triamminkobalt(III)]sulfat-8-Hydrat

The crystal structure of Di-μ-sulfato-μ-hydroxo-bis[triamminecobalt(III)] sulfate 8-hydrate has been determined from three-dimensional x-ray data collected by counter techniques. The structure was refined using 2515 independent reflections and the refinement converged to a conventional R factor (on F) of 3.8%. The compound crystallizes in the monoclinic space group C—P2/a, a = 14.122(9), b = 9.858(2), c = 18.81(2) Å, β = 139.3(4), Z = 2, d_obsd = 2.086 g/cm³ and d_calc = 2.14 g/cm³. Within the cation two bidentate SO₄-ligands form bridges between two cobalt atoms. There are two types of S? O bonds (1.50 Å endocyclic, 1.45 Å exocyclic).