Oxidative cyclization of 2-pyrrolidinyl-acetamide and 2-pyrrolidinyl-propionamide local anaesthetics

2 - Pyrrolidinyl - acetamide and -propionamide local anaesthetics (1a–d) on oxidation with mercuric acetate, potassium hexacyanoferrate(III) and potassium permanganate underwent oxidative cyclization to give new bicyclic compounds, hexahydro - 1H - pyrrolo[1,2 - a]imidazolin - 2 - ones (2a–d). The propionamides (1c–d) yielded mixtures of the two possible diastereoisomers of 2c and 2d. These were separated; in solution and above their melting points they epimerized via ring opening and reclosure between the 7a-carbon and 1-nitrogen atoms.     

Isolation,properties and association phenomena of alkaline salts and their crown complexes of a radical anion

The obtention of (tetradecachloro-4-oxidotriphenylmethyl)^–. M⁺ (M=Li, Na, K, n-Bu₄N) salts in ethereal solution and the isolation of some alkaline complexed salts (M=Li-12C4, Na-18C6, K-18C6, K(THF)₁–(H₂O)_3–4, n-Bu₄N) are described and discussed. The association phenomena of these salts has been studied by electronic spectroscopy, osmometry and electron spin resonance. Linear correlations between radii counterions and the position maxima of the electronic spectra bands permit the study of the species present in solution (free ions, ion pairs and quadrupolar aggregates).     

Die katalytischen Reaktionen bei der Spurenanalyse und die Untersuchung ihrer Mechanismen. II Untersuchung der Tiron—H2O2-Reaktion

Zusammenfassung Die Oxydation von Tiron durch H₂O₂ in basischem Milieu wird durch Kobalt stark katalysiert. Die katalysierten Vorgänge sind p_H-abhängig. Im p_H-Bereich 9 bis 11 entsteht ein rotes Oxydationsprodukt unbekannter Struktur; wahrscheinlich handelt es sich um ein o-Chinonderivat. Mit Hilfe der katalytischen Reaktion können 10^–4 g Kobalt/5 ml nachgewiesen werden. In diesem p_H-Bereiche stabilisiert Tiron H₂O₂ bei 100° C, bei 40° C jedoch katalysiert es — in Abhängigkeit von der Konzentration des Tirons — den Zerfall des H₂O₂. Der Effekt spielt im Mechanismus der katalysierten Reaktion wahrscheinlich eine Rolle, doch können die Zusammenhänge an Hand der bisher veröffentlichten Angaben nicht klar gedeutet werden. Der die Reaktion begleitende bzw. ihr folgende Nebenvorgang kann auf den katalytischen Zerfall des H₂O₂ · OOH-Komplexes zurückgeführt werden. Zwischen p_H 7 und 9 entsteht bei der katalysierten Reaktion Semichinon, über p_H 11 oxydiert Tiron das Semichinon unter Ringspaltung und Abspaltung von 1 Mol Sulfat zu Verbindungen, die Säurecharakter tragen.

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Summary The oxidation of Tiron by H₂O₂ in basic milieu is strongly catalyzed by cobalt. The catalyzed reactions are p_H-dependent. A red oxidation product of unknown structure results in the p_H range 9 to 11; probably it is ano-quinone product. As little as 10^–4 g cobalt/5ml can be detected by this catalytic action. In this p_H region, Tiron stabilizes H₂O₂ at 100° C, but at 45° C it catalyzes the decomposition of H₂O₂, in relation to the concentration of the Tiron. The effect probably plays a rôle in the mechanism of the catalyzed reaction, but the up to now published informations are not sufficient to clarify the relationships. The auxiliary process, accompanying or following the reaction, can be attributed to the catalytic decomposition of the H₂O₂-OOH^– complex. Semiquinone is produced by the catalytic reaction between p_H 7 and 9, above p_H 11, the Tiron oxidizes the semiquinone with opening of the ring and splitting off of 1 mol of sulfate yielding compounds which have an acidic character.

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Résumé L'oxydation du Tiron par H₂O₂ en milieu basique est fortement catalysée par le cobalt. Les processus de catalyse dépendent du p_H. Dans le domaine de p_H de 9 à 11, il apparaît un produit d'oxydation rouge, de structure inconnue; il s'agit probablement d'un dérivé de l'o-quinone. La réaction catalytique permet de déceler 10^–4 g cobalt/5 ml. Dans ce domaine de p_H, à 100° C le Tiron stabilise l'eau oxygénée et à 45° C, suivant sa concentration, il catalyse la décomposition de l'eau oxygénée. L'effet joue probablement un rôle sur le mécanisme de la réaction catalysée; on ne peut pourtant pas interpréter clairement ces relations au moyen des indications publiées jusqu'ici. Le processus secondaire qui accompagne la réaction ou qui la suit, peut être ramené à la décomposition catalytique du complexe H₂O₂-OOH^–. Entre p_H 7 et 9, la réaction catalysée donne naissance à une semiquinone; au-dessus de p_H 11, le Tiron oxyde la semi-quinone avec ouverture du cycle et élimination d'une mole de sulfate ce qui donne ensuite des composés qui portent le caractère acide.

     

Photooxidative treatment of sulfurous water for its potabilization

The feasibility of potabilization of sulfurous water was investigated by photochemical oxidation processes using a batch photoreactor and a continuous-flow photoreactor, equipped with UV lamps of 1000 W and 1500 W, respectively. Additionally, two advanced processes of oxidation were applied i.e. with a use of a UV light/H2O2/air and UV light/H2O2/O3/air. These two processes were compared for their efficiency to the direct oxidation process where ozone is used in the absence of UV light. Results obtained for both advanced processes showed better oxidation than takes place by ozone in the absence of UV light. After the photooxidation processes, different processes for the absorption or precipitation of sulfates were investigated to comply with the World Health Organization (WHO) norm that demands a limit of < or =250 mg L(-1) of SO4(2-) in drinking water. Additionally, reverse osmosis was simulated using Osmonics Inc. software to predict the feasibility of lowering the salt concentration below WHO limits.     

Etude comparative des photoréactions de thiophènes et de furannes avec la propylamine

Mechanisms explaining the formation of pyrroles obtained by UV irradiation of thiophen, the two methylthiophens, the four dimethylthiophens, 2-phenylthiophen, furan, the two methylfurans, and 2,4- and 2,5-dimethylfuran in the presence of n-propylamine are discussed. A comparison of the structure of thiocarbonyl and carbonyl intermediates most likely to be formed by UV irradiation of the substrates with the structure of the experimentally obtained pyrroles indicates that the formation of pyrroles from thiophenes and furans seems to follow mechanisms described in Schemes 1 and 4.     

Die kolorimetrische Bestimmung von Siliciumspuren in Molybdän und Molybdänverbindungen

Zusammenfassung Die kolorimetrische Siliciumbestimmungsmethode vonMillner undNeugebauer wurde für die Bestimmung von Siliciumspuren in Molybdän und seinen Verbindungen modifiziert. Die Ungültigeit des Lambert-Beerschen Gesetzes konnte auf Zeitreaktionen, das heißt auf kinetische Gründe zurückgeführt werden. Wenn man diese berücksichtigt und der Ausbildung der gelblichen Heteropolysäure und ihres Reduktionsproduktes, der blauen Heteropolyverbindung, genügend Zeit läßt, erhält man eine gerade verlaufende Eichkurve und reproduzierbare Ergebnisse.

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Summary The colorimetric determination of silicon proposed byMillner andNeugebauer for the determination of traces of silicon in molybdenum and its compounds was modified. The curvature of the calibration curve could be ascribed to time reactions, i. e. to kinetic causes. If they are taken into account, and sufficient time is allowed for the development of the yellowish heteropoly acid and its reduction product, the blue heteropoly compounds, a straight calibration curve and reproducible findings are obtained.

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Résumé On a modifié la méthode de dosage colorimétrique du silicium deMillner etNeugebauer afin de doser des traces de silicium dans le molybdène et dans ses composés. On a pu attribuer à l'évolution au cours du temps, c'est-à-dire à une base cinétique, la courbure de la courbe d'étalonnage. En tenant compte de ceci et en laissant suffisamment de temps à la formation de l'hétéropolyacide jaunâtre et de son produit de réduction, l'hétéropolyacide bleu, la courbe d'étalonnage est alors une droite et les résultats sont reproductibles.

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Wir danken auch an dieser Stelle herzlichst FrauE. Diós für die Ausführung zahlreicher Messungen, HerrnJ. Szabó für die Überlassung des Spektralphotometers und Herrn DirektorF. Kmüves für die Genehmigung der Publikation.     

A fluorimetric study of pindolol and its complexes with cyclodextrins

Spectrofluorimetric characteristics of pindolol have been investigated with the aim of using this technique for analytical determinations. Other monosubstituted indole derivatives, 4-methoxy and 5-methoxyindole, have been also studied for comparative purposes. Corrected excitation and emission wavelengths in different solvents are reported and the effect of solvent on the Stokes shifts of these compounds has been analysed using the Lippert equation. In addition, the Stokes shift of pindolol has been determined in dioxan-water solvent mixtures and the presence of specific solvent effects is discussed. The fluorescence of pindolol is pH dependent, the quantum yields determined in water are lower than those in other solvents. With respect to the sensitivity, it has been found that the detection limits in aqueous solutions are improved in the presence of beta and methyl-beta-cyclodextrin. Finally, a fluorimetric analysis of the interaction between pindolol and different cyclodextrins has been carried out in order to determine the apparent stability constants of the complexes and the thermodynamic parameters associated to complexation.     

Composition and thermal stability of SiO2-based hybrid materials TEOS-MTEOS system

Hybrid materials with different amounts of organics permanently bound on the inorganic network obtained in the TEOS-MTEOS (tetraethoxysilan-methyltriethoxysilan) system are used for obtaining coatings with different optical and mechanical properties. To study the thermal stability of the mentioned materials, compositions with different molar ratios of the precursors were prepared. The influence of the solvent and water amounts on the gelation process was also investigated. The gels obtained were characterised by IR spectrometry and their decomposition temperatures were determined by DTA/TG. Thermal stability of the gels is rather influenced by their composition than the conditions of the gelation process. This revised version was published online in July 2006 with corrections to the Cover Date.     

Culture conditions dictate protease and tannase production in submerged and solid-state cultures of Aspergillus niger Aa-20

Undesirable protease production by Aspergillus niger Aa-20 in submerged culture and solid-state culture was evaluated using different concentrations of tannic acid as sole carbon source in a model system designed for tannase production. Protease production was found to be dependent on the culture system used (submerged culture or solid-state culture) and on the initial tannic acid concentration. Expression of protease activity in submerged culture was higher (up to 10 times) than activity obtained in solid-state culture, using identical culture medium composition. In submerged culture, the lowest final protease activity (0.13 IU) was obtained with the highest tannic acid concentration, while in solid-state culture protease activity was not affected by changes in initial substrate concentration. Absence of detectable proteolytic activity in solid-state culture is related to high production of tannase enzyme. Hence, the use of solid-state culture for fungal enzyme production may allow for higher and more stable enzyme titers present in culture extracts.     

Evaluation of the residual stability of polyurethane automotive coatings by DSC

Degradation of poly(ester-urethanes), poly(ether-urethanes) and poly(acrylic-urethanes), as a base for automotive paintings in interior applications, has been studied by DSC. The samples were clearcoat and black-pigmented paints, unstabilized and stabilized with HALS Tinuvin 292, UV absorber Tinuvin 1130 and antioxidant Hostanox O3, exposed to weathering in Xenotest and in Arizona desert. From the dependences of oxidation onset temperature on the heating rate, the kinetic parameters enabling to calculate the oxidation induction time for a chosen temperature have been obtained. From the values of oxidation induction time, the protection factors of the additives and the residual stability of the polymer after an ageing stress has been evaluated. It has been shown that the equivalence between the two methods of weathering depends on the polymer composition. A new criterion for the evaluation of synergism/antagonism of additives in the stabilizing mixture has been proposed.