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41.
Aminoglutethimide [3-(4-aminophenyl)-3-ethylpiperidine-2,6-dione] has been used clinically in the treatment of metastatic breast carcinoma. Inhibition of tumor growth is due to interference with estrogen biosynthesis. However, its action is not specific and its metabolism gives rise to toxic and non-inhibitory metabolites. We sought to explore the impact of relocating the amino group in aminoglutethimide to the ethyl side chain. To that end, we now report the synthesis and aromatase-inhibitory activity of 3-(2′-N,N-diethylamino)ethyl-3-phenylpiperidine-2,6-dione 5. The introduction of the amino functionality on the ethyl group is accomplished via reductive animation of aldehyde 8, prepared in three steps from benzyl cyanide. The synthetic route presented can be used for the preparation of related derivatives of aminoglutethimide. 相似文献
42.
On the basis of recently published electrochemical measurements, the charge transfer efficiency within CdSe nanocrystal/conducting polymer heterojunction composites was investigated by means of luminescence interaction strength. It was found that poly[2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene] and poly-9-vinylcarbazole luminescence was not totally quenched by nanocrystals, whereas poly-3-octylthiophene and polyvinylpyrrolidone was completely quenched. In case of poly-3-hexylthiophene, the nanocrystal luminescence was quenched. The results are in complete agreement with the electrochemical findings and thus, the CdSe nanocrystal/Polyvinylpyrrolidone composite should be a promising material for electroluminescent devices. 相似文献
43.
Summary The solution conformations of 1,4-diaryl-tetrahydro-1H,3H-furo[3,4-c]furans were determined by means of the LIS technique using a modified LIS-simulation program specially designed for the requirements of the aromatic 1,2,3-trimethoxy arrangement as a bidentate coordination site for the NMR shift reagent. The resulting geometries were confirmed by force field calculations (MM2-87) and compared with X-ray derived structures. Reliable data for the conformations in solution allowed a quantitative estimation of the circular dichroism based on the coupled oscillator model.
Lanthanideninduzierte Verschiebungen von aromatischen 1,2,3-Trimethoxy-Verbindungen: Konformationsanalyse von Tetrahydrofurofuran-Lignanen in Lösung
Zusammenfassung Es wurden mittels der LIS-Technik die Konformationen von 1,4-Diaryl-tetrahydro-1H,3H-furo[3,4-c]furanen in Lösung bestimmt. Dazu mußte ein modifiziertes LIS-Simulationsprogramm entworfen werden, das auf die besonderen Verhältnisse der aromatischen 1,2,3-Trimethoxy-Gruppierung eingeht, welche in den untersuchten Verbindungen als zweizähnige Koordinationsstelle für das NMR-Verschiebungsreagens fungiert. Die resultierenden Geometrien wurden mittels Kraftfeldrechnungen (MM2-87) überprüft und soweit vorhanden auch mit Röntgenstrukturdaten verglichen. Für die Lösungskonformationen wurde eine quantitative Abschätzung des Circulardichroismus auf der Basis des Modells für gekoppelte Oszillatoren durchgeführt.相似文献
44.
Gerald Kainz und Eugen Wachberger 《Fresenius' Journal of Analytical Chemistry》1966,222(2):278-282
Zusammenfassung Zur Bestimmung des Sauerstoffs wird die organische Probe in Helium-Atmosphäre gecrackt; die sauerstoffhaltigen Crackprodukte werden über Kohle zu Kohlenmonoxid konvertiert. Um das Kohlenmonoxid von den übrigen Crackprodukten, wie H2, N2 und CH4 abzutrennen, wird es zu Kohlendioxid oxydiert und danach an einem Molekularsieb bei 20° C durch Adsorption zurückgehalten; H2, N2 und CH4 werden aus der Apparatur gespült. Sobald in der Probeleitung reines Spülgas auftritt, wird das adsorbierte Kohlendioxid durch Erhitzen desorbiert und im Detektor gemessen.
Es ist uns eine angenehme Pflicht, der Shell Austria AG., Wien, insbesondere Herrn Direktor Dipl.-Ing. R. Wallner, für die Gewährung eines Forschungsstipendiums an den einen von uns (E. W.) ergebenst zu danken. 相似文献
Summary For the determination of oxygen the organic sample is cracked in helium atmosphere. Cracking products, containing oxygen, are converted to carbon monoxide by coal. For separation from the remaining cracking products (H2, N2, CH4) carbon monoxide is oxidized and then adsorbed on molecular sieve 5A at 20°C; H2, N2 and CH4 are flushed out. As soon as pure carrier gas flows through the sample pipe, carbon dioxide is desorbed by heating the molecular sieve and flushed to the detector.
Es ist uns eine angenehme Pflicht, der Shell Austria AG., Wien, insbesondere Herrn Direktor Dipl.-Ing. R. Wallner, für die Gewährung eines Forschungsstipendiums an den einen von uns (E. W.) ergebenst zu danken. 相似文献
45.
A network of solar carcinogenic/erythemal ultraviolet radiometers has been established in New Zealand. Daily integrated irradiances of this biologically harmful ultraviolet radiation for 1989, 1990 and 1991 are reported from radiometers located at Wellington (41°S) and Christchurch (43.5°S) and for 1990 and 1991 from the Auckland (37°S) radiometer. Although the monitoring program has not been running sufficiently long to discern any long-term changes in levels of solar ultraviolet radiation, shorter term trends are apparent, which are attributed to a seasonal cycle in levels of ozone at midlatitudes and changes in atmospheric aerosols. 相似文献
46.
Renate Seidel Birgit Schnautz Gerald Henkel 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》1996,108(15):1836-1839
47.
Patrizia Calaminici Victor D. Domínguez-Soria Gerald Geudtner Elizabeth Hernández-Marín Andreas M. Köster 《Theoretical chemistry accounts》2006,115(4):221-226
The parallelization of the three-center electron repulsion integrals arising from the variational fitting of the Coulomb potential
is presented. A scheme for dynamical load balancing of the corresponding loop structure is discussed. The implementation in
the density functional theory program deMon using the message passing interface is described. The efficiency of the parallelization
is analyzed by selected benchmark calculations 相似文献
48.
Antonio Currao Nantko Feiken Alceo Macchioni Reinhard Nesper Paul S. Pregosin Gerald Trabesinger 《Helvetica chimica acta》1996,79(6):1587-1591
The ligand (6,6′-dimethoxybiphenyl-2,2′-diyl)bis[3,5-di(tert-butyl)phenylphosphine] ( 1 ) forms an unexpectedly stable hydrido-bis-solvento complex of composition [RuH(isopropanol)2( 1 )]BF4, ( 2 ) under the conditions used in the enantioselective hydrogenation of pyrones. The structure of 2 , determined by X-ray diffraction, represents the first well-characterized chiral five-coordinate bis-phosphine ruthenium-hydride complex stable as a solvento complex, and provides a structural link in the enantioselective pyrone hydrogenation cycle catalyzed by [Ru(OAc)2( 1 )]. Using the arene complex [RuH(p-cymene)( 1 )]BF4 ( 3 ), the chiral pocket of coordinated 1 is shown to be relatively rigid, via NMR spectroscopy. This is reflected in restricted rotation about one of the four P–[3,5-di(tert-butyl)phenyl] P? Cipso bonds at room temperature. 相似文献
49.
50.
Hill M Erker G Kehr G Fröhlich R Kataeva O 《Journal of the American Chemical Society》2004,126(35):11046-11057
The dimethylsilanediyl-bridged ansa-zirconocene dichloride 1, that contains a pendent allyl substituent at a Cp-ring, adds HB(C(6)F(5))(2) to the vinyl group to yield the bifunctional zirconocene/borane complex 2. Substituted benzimidazoles were added to the strongly electrophilic borane moiety as protective groups, which allowed subsequent chloride versus -CH(2)SiMe(3) exchange at zirconium to take place by treatment with the respective alkyllithium reagent. Alternatively, the introduction of active sigma-ligands at zirconium is carried out first, followed by the hydroboration reaction. This route was followed for the synthesis of the diphenyl-ansa-zirconocene/borane complex 12. Complex 12 reacts slowly in solution by intramolecular electrophilic attack of the borane at its adjacent Cp-ring, followed by deprotonation using a [Zr]-Ph group to yield the zwitterionic complex 14 featuring a borata-tetrahydroindenyl moiety as part of the ansa-metallocene framework. Complex 14 was characterized by X-ray diffraction. It adds PMe(3) at zirconium to yield 15. Thermolysis of 12 with excess PMe(3) leads to the formation of the (aryne)zirconocene complex 18, which is stabilized by PMe(3) coordination to zirconium and PMe(3) addition to boron. N-Methylbenzimidazole adds to the -B(C(6)F(5))(2) unit of 12 to give the 1:1 adduct 19. Thermolysis of 19 at 80 degrees C in benzene solution in the presence of one additional equivalent of N-methylbenzimidazole results in deprotonation of the substrate to yield the sigma-N-methylbenzimidazolyl zirconium complex 20 (as a mixture of two diastereoisomers). An additional N-methylbenzimidazole ligand is bonded to the B(C(6)F(5))(2) unit in this product. 相似文献