Alkylierung ambidenter Heterocyclen-Anionen, 2.Mitt.: Zur Alkylierung von 4-Hydroxy-carbostyrilen

Zusammenfassung Der Lösungsmitteleinfluß bei der Alkylierung von 4-Hydroxy-carbostyrilen (1–3) mit Äthyl- bzw. Methyljodid und Allylbromid wird untersucht. Während inDMF und Äthanol fast ausschließlich O-Alkylierung zu den 4-Alkoxy-carbostyrilen (4–7) eintritt, beobachtet man in wäßr. Alkalien auch die Bildung von C,C-dialkylierten Verbindungen (8–10). 3-Äthyl-4-hydroxy-carbostyril (2) reagiert leichter mit C₂H₅J zum 3,3-Diäthyl-2,4-dioxo-tetrahydrochinolin (8) als das unsubstit. 4-Hydroxy-carbostyril (1). Einige in der Literatur als 3,3-disubstit. 2,4-Dioxo-tetrahydrochinoline formulierte Verbindungen werden als Carbostyril-4-äther erkannt.

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The influence of the solvent in the alkylation reaction of 4-hydroxyquinol-2-ones (1–3) with various alkyl halogenides has been studied.DMF and ethanol favor high yields of O-alkylated products (4–7), in aqueous alkali, however, carbon alkylation successfully competes with O-alkylation, affording a substantial amount of 3.3-disubstituted 2.4-dioxo-tetrahydro-quinolines (8–10). The reexamination of a patent showed that some compounds previously described as 2.4-dioxo-tetrahydro-quinolines actually are carbostyril-4-ethers.

     

Etude des métastannates de cadmium par spectrographie d'absorption infrarouge entre 5 et 40μ. Solutions solides entre l'oxyde d'étain et Poxyde de cadmium

Résumé Par chauffage à 1000° de mélanges d'oxyde stannique et d'oxyde de cadmium en proportions diverses, comme par déshydratation de précipités mixtes des hydroxydes correspondants, il se forme une série de solutions solides de l'oxyde de cadmium dans l'oxyde d'étain. Elles sont solubles dans l'acide chlorhydrique et présentent un spectre d'absorption infrarouge caractéristique que l'on a comparé avec celui des 2 métastannates de cadmium CdSnO₃, l'un de type ilménite, l'autre de type perovskite.

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Summary By heating various mixture of stannic oxide and cadmium oxide to 1000° C, a series of solid solutions of cadmium oxide in stannic oxide results as is the case when mixed precipitates of the corresponding hydroxides are dehydrated. They are soluble in hydrochloric acid and yield a characteristic infrared absorption spectrum that was compared with that of the two cadmium métastannates CdSnO₃, one of the ilmenite type, the other of the perovskite type.

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Zusammenfassung Erhitzt man verschieden zusammengesetzte Gemische von Zinnoxid und Cadmiumoxid auf 1000° C oder werden Mischfällungen der entsprechenden Hydroxide dehydratisiert, so entsteht eine Reihe fester Lösungen von Cadmiumoxid in Zinnoxid. Sie sind in Salzsäure löslich und zeigen ein charakteristisches Absorptionsspektrum im IR. Dieses wurde mit dem Spektrum zweier Cadmium-Metastannate (CdSnO₃) vom Typus des Ilmenits bzw. Perovskits verglichen.

     

Synthesen von Heterocyclen, 72. Mitt.: 4-Phenyl-3,4-dihydro-carbostyrile aus α-Cyanzimtsäureamiden

Zusammenfassung Bei der Reaktion vonSchiffschen Basen mit Cyanacetylchlorid entstehen über labile Addukte -Cyanzimtsäure-anilide, die in Gegenwart von AlCl₃ zu Derivaten des 3-Cyan-4-phenyl-3,4-dihydrocarbostyrils reagieren. Aus diesen kann durch Verseifung die Cyangruppe eliminiert werden.

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The reaction of azomethines with cyanoacetyl chloride leads via instable adducts to -cyanocinnamic anilides, which with AlCl₃ undergo cyclisation to derivatives of 3-cyano-4-phenyl-3,4-dihydrocarbostyrils. The cyano group in these compounds can be removed by hydrolysis and decarboxylation.

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Herrn KollegenO. Hromatka, Wien, mit den besten Wünschen zum 60. Geburtstag.     

Liquid-liquid extraction of cadmium(II) from aqueous thiocyanate solutions with liquid anion-exchangers

An investigation has been made on the system liquid anion-exchanger-Cd(II)-NCS⁻. The influence of the acidity and thiocyanate concentration of the aqueous phase on the extraction has been studied. Using various methods of analysis, it has been shown that the complex anion present in the organic extracts is Cd(NCS) ₄ ²⁻ . Details are given concerning the removal of traces of Zn(II) from Cd(II)-containing solutions, and the quantitative separation of Cd(II) from Cr(III).     

On the biological importance of the hydrogen bond breaking potency of fluorocarbons

Fluorocarbons containing higher halogens have the potency of breaking certain hydrogen bonds in solutions. The relative strength of this potency varies in the series F < Cl < Br < I and the presence of hydrogen atoms in the fluorocarbon increases it. There is a striking parallelism between the hydrogen bond breaking and the anaesthetic potency of these molecules. It is suggested that the breaking of hydrogen bonds is an important step in the mechanism of anaesthesia.     

Etude de la structure de l'iodatochromate de potassium par spectrographie d'absorption infrarouge entre 3 et 35μ

Résumé Dans le spectre d'absorption infrarouge de l'iodatochromate de potassium K[(CrO₃)(IO₃)], on peut identifier la présence de bandes de vibration de valence de ponts Cr-0-I à 508 et680 cm^–1.

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Summary The infrared absorption spectrum of potassium iodatochromate K(CrO₃)(IO₃) contains vibration bands of the valence bridges Cr-O-I at 508 and 680 cm^–1.

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Zusammenfassung Im Infrarot-Absorptionsspektrum des Kaliumjodatochromats lassen sich Banden der Valenzschwingungen der Atomgruppe Or-O-J bei 508 und 680 cm^–1 nachweisen.

     

Use of non-segmented flow,post-columns reaction detection with miniaturized HPLC systems

Summary The use of non-segmented flow, post-column reaction detection is evaluated for use with miniaturized HPLC. Non-segmented open-tubular reactors with internal diameters 0.1 mm to 0.25 mm and packed-bed reactors with internal diameters of 1 mm, filled with 5 and 10 m particles are evaluated theoretically and experimentally with respect to band broadening and pressure drop characteristics. An integrated system consisting of miniaturized HPLC (1 mm i. d.) columns and compatible hardware is described. An example of the separation of catecholamines is given.     

Arzneimittel- und Drogenscreening aus Urin mittels DC unter besonderer Berücksichtigung von Reagentien mit geringer toxischer Belastung für Laborpersonal und Umwelt

Summary A technique is presented for the extraction of free and conjugated drugs and related compounds out of small quantities of urine. The method is designed in such a way that many samples can be tested for a great number of substances at the same time. Furthermore, we tried to achieve a high quality analysis using when ever possible chemicals with relatively low toxicity to men and environment. Therefore we avoided e.g., halogenated hydrocarbons. The detection of the substances is only performed by thin-layer chromatography (TLC) using well known reagents, like ninhydrin, Dragendorff, iodoplatinate and ferric chloride solutions. If necessary, the extracts can also be used with other Chromatographic techniques, particularly with GC/MS, if a substance has to be clearly identified. Approximately 500 authentical urines have been analyzed in a 1 year period using the method described. We found about 75 different substances. These results are presented in a table.     

Coupling of narrow-bore liquid chromatography to thin-layer chromatography : Part I. Interfacing

The coupling of liquid chromatography (l.c.) on narrow-bore columns to thin-layer chromatography (t.l.c.) is described. The effluent from a l.c. column can be deposited on a t.l.c. plate after a normal-phase or reversed-phase separation without serious loss of chromatographic information. Both silica and alkyl-modified silica plates can be used for storage. The interface is a fused silica capillary which connects the column outlet to the spray jet assembly of a Linomat applicator for t.l.c. The stored chromatogram can serve as starting point for a new separation, but also allows the use of detection principles which are normally not compatible with l.c. The chromatography of some polynuclear aromatic hydrocarbons is used to illustrate the possibilities of the combinations.     

Züchtung von Einkristallen ternärer Lanthanoid-Vanadium(III)-oxide LnVO3 durch Schmelzflußelektrolyse

Growth of Single Crystals of Ternary Rare Earth Vanadium(III) Oxides LnVO₃ by Flux Electrolysis A simple method for growing single crystals of rare earth vanadium(III) oxides LnVO₃ (Ln = La, Sm, Gd, Dy, Er, Yb) by cathodic reduction, starting from vanadium(V) oxide, in a flux of sodium tetraborate and sodium fluoride at T = 1000 K is described. The products were obtained as black, prismatic crystals, suitable for X-ray investigations etc. They were characterized by electron microprobe analyses and by X-ray powder investigations.