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991.
Heinz Falk Karl Grubmayr Gerhard Kapl Norbert Müller Ulrich Zrunek 《Monatshefte für Chemie / Chemical Monthly》1983,114(6-7):753-771
2,3-Dihydrobilatrienes-abc substituted analogous to the natural chromophor of phytochrome may exhibit diastereomerism at the exocyclic double bond of the unsaturated lactam ring. Their properties are comparable to the previouslystudied bilatriene-abc diastereomers. At the exocyclic double bond of the saturated lactam ring however, diastereomers could only be prepared for thermodynamic reasons. The spectroscopic properties of the various diastereomers of five compounds were recorded and are discussed with respect to their utility in structural studies of the natural pigment system. 相似文献
992.
Braun G Inagaki K Estabrook RA Wood DK Levy E Cleland AN Strouse GF Reich NO 《Langmuir : the ACS journal of surfaces and colloids》2005,21(23):10699-10701
Electrostatic assembly of cationic nanoparticles onto the negatively charged backbone of double-stranded DNA has been shown to produce one-dimensional chains with potential use as nanoelectronic components. In this paper, micron long DNA templates stretched on aminosilane- and hexamethyldisilazane-modified silicon surfaces are used to assemble 3.5 nm gold nanoparticles passivated with cationic thiocholine. Atomic force microscopy is used to analyze the density and defects along the approximately 5 nm high structures, with comparison between positively charged and neutral surfaces. Low background adsorption of nanoparticles is facilitated by both these surface chemistries, while the neutral surface yields a more densely packed assembly. 相似文献
993.
[reaction: see text] The diastereoselective synthesis of highly functionalized gamma-lactams starting from 4-(1-bromoalkyl)-2-azetidinones via N-acyliminium intermediates is described. The carbenium ions, formed by dissociation of bromide from 4-(1-bromoalkyl)-2-azetidinones in polar medium, are converted via a ring expansion toward N-acyliminium ions, which are susceptible to attack of oxygen, nitrogen, and carbon nucleophiles. In this way, a variety of 5-hydroxy-, 5-alkoxy, 5-cyano-, 5-allylamino- and 5-azido-4,4-dimethyl-2-pyrrolidinones were synthesized. It was found that dehydrobromination of 4-(1-bromoalkyl)-2-azetidinones constituted an important side reaction when the title reactions were carried out in DMSO. When THF was used as a solvent, generally no dehydrobromination was observed, implying that higher yields of gamma-lactams were obtained in THF compared to reactions performed in DMSO. Also substituents of the 4-(1-bromoalkyl)-2-azetidinones play an important role concerning the obtained diastereoselectivity and the degree of dehydrobromination. 相似文献
994.
Zusammenfassung Die Papierchromatographie der Pyridinmono- und-dicarbonsäuren wurde durch Einführung einer größeren Anzahl von Lösungsmittelgemischen so weit ausgearbeitet, daß jede dieser Säuren mit Sicherheit identifiziert werden kann. Es ist jetzt möglich, Oxydationen von Alkylpyridinen mit 1 bis 2 mg (mittels Permanganat) durchzuführen und in der Oxydations-flüssigkeit ohne weitere Isolierungs- oder Reinigungsmaßnahmen unmittelbar die vorhandenen Pyridincarbonsäuren zu identifizieren.Versuche, einige Alkylpyridine direkt, also ohne Oxydation, papierchromatographisch zu trennen, zeigten positive Ergebnisse.Die hier veröffentlichten Ergebnisse wurden, soweit jeweils schon vorhanden, in Vorträgen bei der Hauptversammlung des Vereines Österr. Chemiker in Klagenfurt (20. September 1954) bzw. beim XIV. Kongreß für reine und angewandte Chemie in Zürich (26. Juli 1955) mitgeteilt. 相似文献
995.
996.
McLachlan LJ Hinchley SL Robertson HE Rankin DW Mitzel NW 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(7):1411-1417
The molecular structure and conformation of 1,1,1,4,4,4-hexachloro-1,4-disilabutane in the gas-phase have been determined by electron diffraction and computational methods. The lowest-energy conformation has the trichlorosilyl groups anti to one another. The gauche conformation also has a shallow potential minimum, but lies about 19 kJ mol-1 above the anti form. Calculations on related butane derivatives, in which terminal methyl groups have been replaced by CCl3, SiH3 and SiCl3 groups, reveal that the conformational preferences are primarily caused by steric interactions between the terminal groups, and that it is the presence of chlorine atoms that destabilises gauche conformations. The electronegativity of the chlorine atoms has only small effects, mainly limited to the SiCl bond lengths. 相似文献
997.
To value a stoichometric asymmetric synthesis it is important for a synthetic chemist to gain information about those structural elements of a chiral auxiliary which are responsible for high diastertomeric excesses in a particular reaction. Furtheron it is desirable to have detailed knowledge about the mechanism of the chirality transfer. In this paper an empirical relation is formulated for the correlation of structural variations of a chiral auxiliary and its influence of the diastereomeric excess in the photochemical oxetane formation in correspondance to the Ugi/Ruch concept. For this purpose we use a Linear Free Energy Relationship (LFER) which we have adjusted to reaction (2) in order to obtain quantitative information about the selectivity of this reaction on the basis of special parameters of the auxiliary applied. 相似文献
998.
Heinz Falk Norbert Müller Michael Ratzenhofer Karl Winsauer 《Monatshefte für Chemie / Chemical Monthly》1982,113(12):1421-1432
Anaerobic irradiation of bilibrubin in the region of the main absorption band produces the diastereomers of (Z,E)- and (E,Z)-configurations with high quantum yield. The structure of these photobilirubins is proven by a chemical correlation with the corresponding diastereomers of biliverdindimethylester characterised before. Their1H-NMR spectroscopic features have been recorded and are discussed.
Die Struktur der Photobilirubine
Zusammenfassung Anaerobe Bestrahlung von Bilirubin im Gebiet der Hauptabsorptionsbande ergibt in hoher Quantenausbeute die Diastereomeren der Konfigurationen (Z,E) und (E,Z). Die Struktur dieser Photobilirubine wird durch eine chemische Korrelation mit den entsprechenden bekannten Diastereomeren des Biliverdindimethylesters bewiesen. Die1H-NMR-Daten der Diastereomeren werden diskutiert.相似文献
999.
The separation of selected lignin/humic substance (HS) degradation compounds by capillary electrochromatography (CEC) with a methacrylate-based monolithic column and a conventional column packed with 5 microm octadecyl silica (ODS) particles is presented. The effects of organic modifier concentration, pH of the mobile phase, ionic strength, applied voltage, and temperature on the separation were investigated to determine the optimal separation conditions. With the increase of pH in the mobile phase, some of analytes start to ionize and both chromatographic partition and electrophoresis can play roles in separation simultaneously. Accordingly, different selectivity from high-performance liquid chromatography (HPLC) and capillary electrophoresis (CE) could be achieved. The performances of both kinds of columns were compared. The results showed that the peaks of compounds obtained on the former column were much wider than those on the latter one, although good separation efficiency of alkylbenzenes could be readily achieved; the most probable reasons for this behavior and method to solve this problem were briefly discussed. The CEC of a soil fulvic acid with a monolithic column produced partly resolved broad bands; by means of nuclear magnetic resonance (NMR) analysis a wide range of oxygen derived aromatic substitution patterns was found with prominent contributions from phenolic and carboxylic groups. 相似文献
1000.
[reaction: see text] An efficient and straightforward route toward 3,4-cis-4-isopropenylazetidin-2-ones was developed from 4-(1-chloroalkyl)azetidin-2-ones. Starting from the latter beta-lactams, a new synthesis of pyrrolidin-2-ones was achieved. When 4-isopropenylazetidin-2-ones were treated with bromine in dichloromethane, diastereoselective electrophile-induced ring expansions toward 5-bromopyrrolidin-2-ones were performed. Further oxidation of 3-benzyloxypyrrolidin-2-ones with bromine toward 3-bromopyrrolidin-2-ones was also established. When 4-isopropenyl-beta-lactams were added to a mixture of NBS and TMSN(3), 5-azidopyrrolidin-2-ones were obtained in moderate to high yields. 相似文献