Gemeinsame Einwirkung von elementarem Schwefel und Äthylenimin auf Ketone, 2. Mitt.

Zusammenfassung Bei der gemeinsamen Einwirkung von Schwefel und Äthylenimin auf 4-Heptanon, Cyclopentanon, Cyclohexanon und Cyclooctanon bilden sich in glatter Reaktion 5,6-Dihydro-4H-1,4-thiazine (3–6). Als Nebenprodukte von3, 4 und5 fallen die dem jeweiligen Keton zugrunde liegenden 2,2-dialkylierten Thiazolidine (7–9) an. Bei Einsatz von Phenylisopropylketon in diese Reaktion wird dagegen das 2-Isopropyl-2-phenylthiazolidin (12) zum Hauptprodukt, während das entsprechende 5,6-Dihydro-2H-1,4-thiazin (11) nur in untergeordnetem Maße entsteht.Die Reaktionsmechanismen sowohl der 5,6-Dihydro-1,4-thiazin-als auch der Thiazolidin-Bildung werden diskutiert.Die Umsetzung der 5,6-Dihydro-1,4-thiazine (1, 3–5, 11) mit überschüss. Ameisensäure führt zu N-Formylthiomorpholinen (13–17), die sich mit verd. HCl glatt zu den entsprechenden Thiomorpholinen (18–22) verseifen lassen.

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Concomitant action of elementary sulfur and gaseous ammonia upon ketones, LXXI. Concomitant action of elementary sulfur and ethylenimine upon ketones, II

The interaction of sulfur and ethylenimine with 4-heptanone, cyclopentanone, cyclohexanone, and cyclooctanone leads to 5.6-dihydro-4H-1.4-thiazines (3–6) in good yields. As byproducts of3, 4 and5 2.2-dialkylated thiazolidines (7–9, resp.) are isolated. When this reaction is carried out with phenyl isopropyl ketone, however, the main product is 2-isopropyl-2-phenylthiazolidine (12), the corresponding 5.6-dihydro-2H-1.4-thiazine (11) is but formed in a small quantity.The mechanisms of the formation of 5.6-dihydro-1.4-thiazines, as well as the formation of the thiazolidines are discussed.Reaction of 5.6-dihydro-1.4-thiazines (1, 3–5, 11) with excess formic acid leads to N-formylthiomorpholines (13–17) which can be easily saponified with dil. HCl to the corresponding thiomorpholines (18–22).

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Herrn Prof. Dr.O. Hromatka mit herzlichen Grüßen zum 65. Geburtstag gewidmet

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70. Mitt.:F. Asinger, H. Offermanns, D. Neuray undF. Abo Dagga, Mh. Chem.101, 500 (1970)

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Teil der DissertationK. H. Lim, Techn. Hochschule Aachen, 1969.

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Teil der DissertationD. Neuray, Techn. Hochschule Aachen, 1969

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1. Mitt.:F. Asinger, H. Offermanns, W. Pürschel, K. H. Lim undD. Neuray, Mh. Chem.99, 2090 (1968).     

Kondensationsreaktionen von α-Aminothionamiden und α-Oxothionamiden

Ohne Zusammenfassung64. Mitt.:F. Asinger, H. Offermanns undP. Krings, Ann. Chem. (im Druck). P. Müller, Teil der Diplomarbeit, Techn. Hochschule Aachen, 1967. H. Andree, Teil der Diplomarbeit, Techn. Hochschule Aachen, 1967.     

Cobalt(III) complexes with aminothiolates

Summary This article describes some complexes of cobalt(III) with -mercaptopropylamine,N, N-dimethyl--mercaptopropylamme andN,N-dimethyl--mercaptoethylamine. The compounds are of stoichiometry [Co(ligand)₃], [Co₃(ligand)₆]_X (X=Cl or Br) and [Co(ligand)₃]X₃ (X=Cl or ClO₄). -Mercaptopropylamine yields both chelated and non-chelated compounds while theN,N-dimethyl derivatives yield only non-chelated complexes. This behaviour contrasts with the results obtained with nickel(II).     

Hexagonal high‐temperature form of aluminium phosphate tridymite from X‐ray powder data

Similar to silica tridymite, AlPO₄ tridymite shows a sequence of displacive phase transitions resulting in a dynamically disordered hexagonal high‐temperature modification. Rietveld refinement reveals that the thermal motions of the tetrahedra can be described either by strongly anisotropic displacement parameters for oxy­gen or by split O atoms. Due to the ordered distribution of aluminium and phospho­rus over alternating tetrahedra, the space group symmetry of high‐temperature AlPO₄ tridymite is reduced with respect to SiO₂ tridymite from P6₃/mmc to P6₃mc.     

Pd-katalysierter Deuterium-Austausch am Octa(silsesquioxan)H8Si8O12 zu D8Si8O12

Pd-Catalyzed Deuterium Exchange of Octa(silsesquioxane) H₈Si₈O₁₂ to D₈Si₈O₁₂ Deuterium exchange on octa(silsesquioxane) H₈Si₈O₁₂ to D₈Si₁₈O₁₂ catalyzed by palladium on carbon is reported.     

Biosynthesis of the Purple Membrane of Halobacteria

Halobacteria are extremely specialized organisms. They live exclusively in saturated solutions of common salt. The cell membrane of these bacteria exhibit insular regions which can be isolated by membrane fractionation. These regions consist of a lipid matrix containing bateriorhodopsin molecules in a hexagonal crystalline arrangement. Bacteriorhodopsin is a deep purple retinal-protein complex (“purple membrane”). The purple membrane functions as a light energy converter.—How can such a differentiated membrane region arise? In vivo studies on the biosynthesis of the purple membrane showed another cell membrane fraction, the so-called brown membrane, to be a biosynthetic precursor. Bacterioopsin (the retinal-free protein) is initially incorporated into the brown membrane and can only form the purple membrane by crystallization in an energy-dependent reaction after prior reaction with retinal. This reaction is reversible. Removal of the retinal by formation of retinal oxime causes the purple membrane regions to disappear. Reconstitution of the bacteriorhodopsin by addition of retinal regenerates the purple membrane.     

Crystal growth and transport rates of GeSe and GeTe in micro-gravity environment

Six vapor transport experiments on the systems GeSe-GeI₄ and GeTe-GeI₄ were performed on Skylab to determine the effects of micro-gravity on crystal growth and transport rates. Based on a direct comparison of crystals and transport data obtained on earth and in space, employing X-ray diffraction, microscopic and etching techniques, the results demonstrate a considerable improvement of the space grown crystals in terms of growth morphology and bulk perfection. The observation of greater mass transport rates than expected in micro-gravity for diffusion-controlled transport could indicate the existence of other transport modes in a reactive solid-gas phase system. The combined results show that the interference of gravity-driven convection with the transport process causes negative effects on crystal growth as observed on earth for otherwise identical conditions. This points to the unique environment of weightlessness for the observation of basic transport phenomena.     

Identification of plastic material parameters with error estimation

In recent years, inverse analysis has become a common approach to typical engineering problems such as model identification. In this contribution, the inverse problem is discussed in light of taking experimental uncertainties into account. This involves in particular the propagation of experimental errors and the analysis of the sensitivity of the model response to variations in the model parameters to be determined. The method is applied to an elasto-viscoplastic material model which is used in the context of electromagnetic high-speed forming. (© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Über Belüftungselemente

Zusammenfassung Diskussion der Forderungen, die sich ergeben, wenn man die Eisenkorrosion in neutralen belüfteten Elektrolytlösungen als reinen diffusionskontrollierten Vorgang, entsprechend dem 1.Fickschen Gesetz betrachtet: Das 1.Ficksche Gesetz ist nur dann anwendbar, wenn sichunter sonst konstanten Bedingungen (Elektrolyt, Widerstand, Elektrodenmaterial) die Variablen Oberfläche, Konzentration des Depolarisators, Dicke der Diffusionszone, ändern. Die Diffusionsstromstärke gehorcht in dem untersuchten Fall demOhmschen Gestz; sie ist stark von dem Bearbeitungszustand der Kathode abhängig. Rechnet man die kathodischen Gewichtsverluste auf Coulombs um, so ist die Summe aus der gemessenen und der berechneten Strommenge konstant; ein Hinweis, daß die depolarisierende Sauerstoffmenge konstant und der Gewichtsverlust an der Kathode ebenfalls durch Sauerstoffdepolarisation erfolgt sein muß.Mit 5 Abbildungen.Herrn Prof. Dr.A. Klemenc zum 70. Geburtstag gewidmet.