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51.
Ccile Pasquier Albert Gossauer Walter Keller Christoph Kratky 《Helvetica chimica acta》1987,70(8):2098-2109
(?)-(4S,16S)-8, 12-bis[de(2-carboxyethyl)]mesourobilin-IIIα hydrochloride ( 8 ) has been synthesized from the enantiomerically pure 1,4,5,10-tetrahydro-1-oxodipyrrin-9-carboxylic-acid precursor 6a whose absolute configuration was determined by X-ray diffraction analysis of the N-[(S)-1-(1-naphthyl)ethyl] carboxamide 7b . The present results prove unequivocally that an (S,S)-configurated urobilin chromophore displays a negative Cotton effect in the VIS absorption range. However, the helicity of the inherently dissymmetric chromophore remains undetermined. 相似文献
52.
Sabine Strohschein Matthias Pursch Heidrun Händel K. Albert 《Analytical and bioanalytical chemistry》1997,357(5):498-502
The separation of cis/trans isomers of β-carotene has been performed with a C30 stationary phase employing 1H NMR spectroscopy as an on-line detection technique. 1D as well as 2D NMR spectra have been recorded in the stopped-flow
mode for the predominant chromatographic peaks. Structural assignment of the five identified isomers was performed via comparison
of simulated 1D 1H NMR spectra on the basis of the structures of β-carotene cis/trans isomers with the experimental data, and also by the analysis of the proton-proton connectivities in the 2D NMR spectra of
three isomers with the highest concentration. The chromatographic retention behaviour of the isomers agreed well with previously
reported data. The advantage of the applied hyphenated coupling technique compared to conventional off-line techniques lies
in the fact that chromatographic separation and NMR detection are performed in a closed system, so that reisomerization of
the separated compounds is inhibited.
Received: 29 May 1996 / Revised: 1 July 1996 / Accepted: 4 July 1996 相似文献
53.
Ph. Albert 《Journal of Radioanalytical and Nuclear Chemistry》1980,55(2):453-462
In this article the research topics dealt with at Research Group for Applications of Nuclear Reactions to Chemical Analysis
(GARNAC) are described. Particular emphasis is laid on the main contribution of the GARNAC to the development and the evolution
of charged particle activation analysis, evolving with the analytical studies performed and with the scientific and technical
progress realized in material and semiconductors science.
相似文献
54.
Albert Fischli 《Helvetica chimica acta》1982,65(8):2697-2708
The olefinic system in 3β-methoxy-4-cholesten-6 a-ol ( 2 ) is reduced using cob (I)alamin ( 1 ( I ); see Scheme 1) as catalyst, aqueous acetic acid as solvent and metallic zinc as electron source (cf. Schemes 2 and 3). Experimental evidence for an attack of 1 ( I ) on both faces of the double bond is presented. By the same catalyst (1 R)-10, 10-dimethyl-2-pinene- 10-carbonitrile ( 9 ) is first transformed to the menthene derivative 11 (see Schemes 4 and 5). The ring opening is then followed by a fast saturation of the disubstituted olefinic system in 11 , and ultimately the remaining double bond is reduced in a slow reaction. The cis-configurated saturated menthane derivative 16 is the main final product ( 16 / 17 ≈ 10:1). 相似文献
55.
Steric factors have been shown to be responsible for the anomalous dehydration of 2-phenylindole-3-carboxamide (1) to 2-phenylindole-3-carbonitrile (3) by lithium aluminum hydride. This steric effect was also reflected in the reactions of 2-phenylindole (4) and its derivatives.
Anomale Dehydratisierung von 2-Phenylindol-3-carbonsäureamid zu 2-Phenyl-indol-3-carbonitril mit Lithiumaluminiumhydrid (Kurze Mitteilung)
Zusammenfassung Es wird gezeigt, daß für die anomale Dehydratisierung von 2-Phenylindol-3-carbonsäureamid (1) zum entsprechenden Nitril3 durch Lithiumaluminiumhydrid sterische Faktoren verantwortlich sind. Dieser sterische Effekt zeigt sich auch bei Reaktionen von 2-Phenylindol (4) und seiner Derivate.相似文献
56.
The asymmetric syntheses of the C-1 sidechains of zaragozic acid A and C are described. Aldol reaction defines the chirality at C-4′and C-5′in two independent routes. Multigram preparation as well as a route amenable to derivatization are highlights of these approaches. 相似文献
57.
A new chiral aminophosphine ligand 6,6′-dimethoxy-2,2′-bis(diphenylphosphinoamino)biphenyl(DMBDPPABP) was prepared and its rhodium complex was found to be an effective catalyst for the asymmetric hydrogenation of amidoacrylic acid and its dervatives.The effects of solvent and reaction temperature on enantioselectivity were also studied. 相似文献
58.
The equilibrium of the heterogeneous reaction between dissolved sodium sulfide and biologically produced sulfur particles has been studied. Biologically produced sulfur was obtained from a bioreactor of a hydrogen sulfide removal process in which the dominating organism is Thiobacillus sp. W5. Detailed knowledge of this reaction is essential to understand its effect on the process. The results were compared with the equilibrium of the reaction of sulfide with ‘inorganic’ elemental sulfur. The equilibrium between dissolved sodium sulfide and biologically produced sulfur particles can be described by an equilibrium constant, Kx, which consists of a weighted sum of constants for polysulfide ions of different chain length, rather than a true single equilibrium constant. For biologically produced sulfur pKx = 9.10 ± 0.08 (21 °C) and 9.17 ± 0.09 (35 °C) with an average polysulfide chain length x = 4.91 ± 0.32 (21 °C) and 4.59 ± 0.31 (35 °C). The pKx value for biologically produced sulfur is significantly higher than for reaction of dissolved sodium sulfide with inorganic sulfur (pKx = 8.82; 21 °C). This difference is probably caused by the negatively charged polymeric organic layer, which is present on biologically produced sulfur but absent with “inorganic” sulfur. Specific binding of polysulfide ions to the organic layer results in a higher polysulfide concentration at the reaction site compared to the bulk concentration. This results in an apparent decrease of the measured equilibrium constant, Kx. 相似文献
59.
A new software-controlled volume-based system for sample introduction in process flow injection analysis was developed. By using a multi-syringe burette coupled with one or two additional commutation valves, the multi-commuted injection of precise sample volumes was accomplished. Characteristics and performance of the injection system were studied by injecting an indicator in a buffered carrier. Three configurations were implemented in order to achieve two different tasks: the single injection of a sample in a two- or three-channels manifold, and the dual injection into different streams. The two channel flow system using the single injection was applied to the determination of free acidity in diluted samples containing high levels of iron(III), by employing the single point titration methodology. The precipitation of ferric hydroxide was prevented using the ammonium and sodium salts of oxalate and acetate as buffer titrant. Methyl Red was employed as indicator. The procedure allows determination of acid concentration in solutions with a Fe(III)/H+ molar ratio up to 0.2. Samples with higher Fe(III)/H+ molar ratios were spiked with a known strong acid at dilution. The three-channel configuration was applied to the determination of ferric ions, using, as reagent, a merging mixture of sulfuric acid and potassium thiocyanate. The double injection system was implemented in series in a single (three-channel) manifold in such a way that a different injection volume and a changed reagent were used for each analyte. It was applied to the separated or sequential determination of free acidity and ferric ions. In this configuration, iron(III) was determined using 0.5-0.7% (w/v) sodium salicylate solution as reagent. The systems can operate at up to 100, 84 and 78 injections per hour, respectively. Determinations on synthetic and process samples compared well with the reference values and procedures. Recoveries of 95-102% with a maximum RSD value of 5.4% were found for acidity. The respective values obtained for iron determinations were 96-105% and 4.3%. 相似文献
60.
Albert Lévai 《Monatshefte für Chemie / Chemical Monthly》1991,122(8-9):691-695
Summary Reactions of 3-arylidenechromanones (1 – 4) and -1-thiochromanones (5 – 8) with thiourea gave thiazines (9 – 16) under acidic and pyrimidine derivatives (17 – 21) under alkaline reaction conditions
Kondensierte Heterocyclen, VI: Umsetzungen von 3-Arylidenchromanonen und-1-thiochromanonen mit Thioharnstoff
Zusammenfassung Die Umsetzung von 3-Arylidenchromanonen1 – 4 und -1-thiochromanonen5 – 8 mit Thioharnstoff liefert unter sauren Bedingungen die Thiazine9 – 16 und in basischem Milieu die Pyrimidine17 – 21.相似文献