Selective hydrogenations of steroids catalyzed by heterogenized Ru complexes

Summary [RuCl₂(PPh₃)₃], [{RuCl₂(TPPMS)₂}₂] and their heterogenized analogs were applied in the selective hydrogenation of 17-keto- and α,β-unsaturated ketosteroids. In basic conditions these complexes selectively hydrogenated the C=O bonds, similarly to the results obtained in the case of α,β-unsaturated aldehydes. A new method was developed for the synthesis of an expensive steroid alcohol, which can be prepared traditionally in a more complicated way.     

Saturated heterocycles, 162 [1]. synthesis and steric structures of 3,4-disubstituted 1,6,7,11b-tetrahydropyrimido[6,1-a]isoquinolin-2-ones

The reaction of 1-(hydrazidomethyl)-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline 3 with aromatic aldehydes yield hydrazones 4a,b or pyrimido[6,1-a]isoquinolines 5a-c depending upon the proportions of the reagents. With ketones, 3 gives only hydrazones 4a-d and 7 , which can be transformed to pyrimidoisoquinolines 10a-e and 11 with aldehydes. The ring closures are stereospecific; the relative configurations were determined by DNOE measurements.     

Novel electroanalytical techniques for pollution analysis

Summary Two new analytical techniques are described. The so-called injection technique operates on evaluating a dynamic concentration signal as a result of following the concentration change in a certain part of a flow-through channel after injecting a sample or reagent at a small volume into the current of an appropriate solution flowing at a constant rate.The second technique, the programmed coulometric titration technique, also uses the flow-through channel principle; that means this novel technique allows the more precise titrimetric way of analysis in flowing solutions. In the case of both techniques potentiometric and voltammetric detectors were involved. Several examples proved the multifold advantages of these techniques for environmental analysis.

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Neue elektroanalytische Verfahren für die Umweltanalyse

Zusammenfassung Zwei neue Methoden werden beschrieben. Die sog. Injektionstechnik wertet ein dynamisches Konzentrationssignal aus, das sich aus der Änderung in einem Durchflußkanal ergibt, wenn Probe oder Reagens in kleinen Volumina in einen konstant fließenden Flüssigstrom injiziert werden. Das zweite Verfahren, die programmierte coulometrische Titration, erlaubt die Anwendung der genaueren titrimetrischen Technik auf fließende Lösungen. Bei beiden Methoden werden potentiometrische und voltammetrische Detektoren verwendet. Mehrere Beispiele zeigen die vielfachen Vorteile dieser Verfahren bei der Anwendung auf die Analyse von Umweltmaterial.

Presented at the 6th Annual Symposium on Recent Advances in the Analytical Chemistry of Pollutants, April 21–23, 1976; Vienna, Austria     

Role of rhenium in bimetallic reforming catalysts

The influence of rhenium on the behavior of a Pt/Al₂O₃ catalyst was studied in n-hexane reaction by means of dilution of the catalyst bed with Re/Al₂O₃. Parallel to activity, selectivity and ageing data obtained in slug pulse and continuous flow reactors, the amount of the surface carbon formed during the reaction was determined and its reactivity in hydrogen atmosphere was also studied. It is suggested that in the presence of rhenium due to the increase in the amount of hydrogen available for hydrogen consuming reactions including hydrodepolymerization of the carbonaceous surface overlayer, the routes of ageing processes are changed, resulting in lower carbon content on the catalyst and less pronounced catalyst deactivation.

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Pt/Al₂O₃ -, Re/Al₂O₃. , , , , . , , , , , , , .

     

Regular Liesegang patterns and precipitation waves in an open system

We investigate the regular and moving Liesegang pattern formation phenomena in an open system. First, simulations have been performed at fixed coupling between the reactive medium and the reservoir, later this control parameter was varied during the simulations resulting in various phenomena. We predicted and monitored for the first time various--dynamically changing--precipitation structures and a spatial hysteresis phenomenon, which is beyond the scope of the Turing instability. The dynamics of the reaction is well detectable using specific quantities: the total amount of precipitate and its center of gravity.     

Synthesis and stereochemistry of stereoisomeric 1,3-benzoxazino-1,3- and -3,1-benzoxazines

Partly saturated 3,1-benzoxazino[1,2-c][1,3]benzoxazines and 1,3-benzoxazino[3,2-c][1,3]benzoxazines were prepared in one-pot syntheses from different cyclic 1,3-aminoalcohols by treatment with salicylaldehyde or 5-bromosalicylaldehyde, followed by formaldehyde. The structures of tetracycles 3a and 5 were determined by means of X-ray diffraction.     

Excess volumes of mixing for some primary alcohols with secondary amines at 293.15 K and 323.15 K

The excess volumes of mixing for methanol and ethanol with secondary amines (diethylamine, di-n-propylamine and di-n-butylamine) have been measured over the whole composition range at 293.15 and 323.15 K. The excess volumes have been fitted to an equation of the type $$V^E /cm^3 mol^{--1} = x \left( {1 - x} \right) \sum\limits_{n = 0}^3 { A_n \left( {1 - 2x} \right)^n } $$ The different temperature dependences of the mixtures were explained by means of the association theory.     

Selective liquid adsorption and structural properties of montmorillonite and its hexadecylpyridinium derivatives

Summary An X-ray diffraction method was used to study the structures of montmorillonites, the surfaces of which were covered to a systematically increasing extent with hexadecylpyridinium (HDP) cations. It was found that, depending on the degree of cover of the surface, the HDP cations form a mono- or bimolecular layer in the interlayer space. A detailed investigation was made of the selective sorption of binary mixtures on montmorillonite and on HDP-montmorillonites with different surface coverages. The adsorption excess isotherms were determined, as were the adsorption capacities from analysis of the isotherms, and also the equivalent specific surface areas.It was established that from benzene-n-heptane mixtures the benzene is adsorbed only on the external surface of montmorillonite, while in the case of organocomplexes it causes moderate disaggregation.From benzene, alcohols with different numbers of carbon atoms are also preferentially adsorbed on the internal surfaces of montmorillonite; with the rise in the number of carbon atoms, the extent of interlamellar adsorption decreases. In the case of HDP-montmorillonites in methanol-benzene mixtures, the adsorption capacity exhibits a monotonous increase with the degree of organopbility in the range under consideration. In the event of optimum organophility the disaggregation of the organocomplex is complete, and the equivalent specific surface area is 764-778 m² · g^–1. The swelling of the organocomplex, which can be characterized by X-ray diffraction measurement, is in close correlation with the interlamellar liquid adsorption. The results show modification of the surface of montmorillonite with HDP cations fundamentally determines the nature and extent of the selective liquid adsorption.

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Zusammenfassung Die Struktur von mit Hexadecyl-pyridinium(HDP)-Kationen im systematisch gesteigerten Maße bedeckten Montmorilloniten wurde mit der Röntgendiffraktions-Methode untersucht. Es wurde festgestellt, daß die HDP-Kationen, von der Bedeckung der Oberfläche abhängend, im Schichtzwischenraum eine mono- bzw. bimolekulare Schicht bilden. Die selektive Sorption binärer Gemische wurde an Montmorilloniten und an HDP-Montmorilloniten verschiedener Bedeckung eingehend untersucht. Es wurden die Adsorptionsisothermen von Flüssigkeitsgemischen und aus deren Analyse die Adsorptionskapazitäten und die äquivalenten spezifischen Oberflächen bestimmt.Es wurde festgestellt, daß aus Benzol-n-Heptan-Gemischen das Benzol nur an der äußeren Montmorillonite-Oberfläche adsorbiert wird, während es bei Organokomplexen eine mäßige Desaggregation verursacht. Die Adsorption von Alkoholen verschiedener Kohlenstoffzahl aus Benzol erscheint auch an inneren Montmorillonit-Oberflächen bevorzugt; mit zunehmender Kohlenstoffzahl nimmt das Ausmaß der interlamellaren Adsorption ab. Bei HDP-Montmorilloniten zeigt die Adsorptionskapazität aus Methanol-Benzol-Gemischen mit zunehmender Organophilität im untersuchten Gebiet eine monotone Steigerung. Im Falle optimaler Organophilität ist die Desaggregation vollständig, die äquivalente spezifische Oberfläche beträgt 764-778 m²/g. Die durch Röntgenn-diffraktionsmessung charakterisierbare Quellung des Organokomplexes steht mit der interlamellaren Flüssig-keitsadsorption in engern Zusammenhang. Unsere Ergebnisse zeigen, daß Charakter und Ausmaß der selektiven Flüssigkeitsadsorption durch die Modifizierung der Montmorillonit-Oberfläche mit HDP-Kationen grundlegend verändert wird.

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With 14 figures and 4 tables     

Coloring linear hypergraphs: the Erdős–Faber–Lovász conjecture and the Combinatorial Nullstellensatz

Designs, Codes and Cryptography - The long-standing Erdős–Faber–Lovász conjecture states that every n-uniform linear hypergaph with n edges has a proper vertex-coloring using...     

Hardy Spaces on the Plane and Double Fourier Transforms

We provide a direct computational proof of the known inclusion where is the product Hardy space defined for example by R. Fefferman and is the classical Hardy space used, for example, by E.M. Stein. We introduce a third space of Hardy type and analyze the interrelations among these spaces. We give simple sufficient conditions for a given function of two variables to be the double Fourier transform of a function in and respectively. In particular, we obtain a broad class of multipliers on and respectively. We also present analogous sufficient conditions in the case of double trigonometric series and, as a by-product, obtain new multipliers on and respectively.