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61.
W.Robert Sinclair J.B. Macchesney P.K. Gallagher P.B. O''Connor 《Thermochimica Acta》1979,30(1-2):225-231
The reaction between SiCl4 and O2 at 1 atm between 25 and 1200°C has been followed by mass spectrometry. Below 600°C no reaction with O2 is noted. Above 600°C the reaction proceeds in two steps. Between 800 and 1000°C the 28Si/32O2 peak height ratio is constant with no evolution of Cl2. It is suggested that silicon oxychlorides are being formed in this temperature regime. Above 1000°C the reaction between SiCl4 and O2 intensifies with concomitant production of Cl2. It is suggested that above 1000°C the reaction SiCl4 + O2 → SiO2 + Cl2 becomes important.
At low temperatures (<800°C) adsorbed H2O and OH groups from the surface of the fused silica tube react with SiCl4 to form HCl. The importance of this reaction decreases with increasing temperature. The increased production of HCl above 1000°C is ascribed to H2O and H2 diffusing from the tube. 相似文献
62.
Isabelle FavierElisabet Duñach 《Tetrahedron》2003,59(10):1823-1830
Mandelic acid and some aryl substituted derivatives were oxidised under molecular oxygen and a catalytic amount of Bi(0). The corresponding aldehydes and/or the carboxylic acids were obtained selectively depending on the nature of the substituent. Aldehydes and α-keto acids were oxidised under the same Bi(0)/O2 system and α-keto acids were proposed as intermediates in the formation of benzoic acid derivatives. 相似文献
63.
64.
65.
Michael Knorr Isabelle Jourdain Carsten Strohmann 《Journal of organometallic chemistry》2005,690(6):1456-1466
Insertion of hexafluorobutyne into the Pt-H bond of the heterobimetallic complexes [(OC)3Fe{Si(OMe)3}(μ-Ph2PXPPh2)Pt(H)(PPh3)] (1a X = CH2; 1b X = NH) yields the σ-alkenyl complexes [(OC)3Fe{μ-Si(OMe)2(OMe)}(μ-Ph2PXPPh2)Pt{C(CF3)C(H)CF3}] (3a X = CH2; 3b X = NH). This insertion reaction is accompanied by dissociation of the platinum bound PPh3 ligand and saturation of the vacant coordination site by a dative μ−η2-Si-O → Pt interaction. Addition of the Pt-H bond of 1a across the triple bond of 3,3,3-trifluoropropyne affords in a regiospecific manner [(OC)3Fe{μ-Si(OMe)2(OMe)}(μ-dppm)Pt{C(CF3)CH2}] (2) having the trifluoromethyl substituent on the α-carbon. Addition of RNC to 3 affords the isocyanide adducts [(OC)3Fe{Si(OMe)3}(μ-Ph2PXPPh2)Pt(CNR){C(CF3)C(H)CF3}] (4a R = t-Bu, X = CH2; 4b R = 2,6-xylyl, X = CH2; 4c R = 2,6-xylyl, X = NH). In dichloromethane solution 3a is gradually transformed into the C4F6-bridged compound [(OC)3Fe(μ-dppm)(μ-CF3CCCF3)Pt(CO)] 5. The Pt-bound carbonyl ligand of 5 is displaced by xylylisocyanide or trimethylphosphite affording the derivatives [(OC)3Fe(μ-dppm)(μ-CF3CCCF3)Pt(CNxylyl)] 6 and [(OC)3Fe(μ-dppm)(μ-CF3CCCF3)Pt{P(OMe)3}] 7. The molecular structures of 4a, 5 and 6 have been determined by X-ray diffraction studies. 相似文献
66.
Ravindra K. Pandeyi † William R. Potter Isabelle Meunier Adam B. Sumlin Kevin M. Smith 《Photochemistry and photobiology》1995,62(4):764-768
Abstract— A first report on the biological evaluation of a series of isomerically pure benzoporphyrin derivatives ( cis- and frarcs-isomers) as methyl esters is described. In preliminary in vivo studies, the n- bexyl ether analogues of both cis- and trans -isomers of benzoporphyrin derivatives were found to be more active than the industrially prepared benzoporphyrin derivative, a mixture of monocarboxylic acids (BPDMA, Quadralogic Technologies, Vancouver). Further studies with 4-de-vinyl-4-(I-hexyloxyethyl) benzoporphyrin derivative showed that, like BPDMA, it had reduced residual skin phototoxicity compared in mice with Photofrin®. The uptake and clearance characteristics of BPDMA were also compared with the 4-(1-hexyloxyethyl)-derivative by in vivo reflection spectroscopy. 相似文献
67.
Hans-Peter Ros Rolf Kyburz Nigel W. Preston Rex T. Gallagher I. Ralph C. Bick Manfred Hesse 《Helvetica chimica acta》1979,62(2):481-487
The revised structure 1 is put forward for peduncularine, the main alkaloid of Aristotelia peduncularis (Labill.) HOOK. F. (Elaeocarpaceae), on the basis of its spectroscopic properties and those of its degradation products, the Hofmann base 3 and the hydrogenation product 4 . Structure 1 represents the relative configuration of the alkaloid. Peduncularine belongs to the class of indole alkaloids with a monoterpene unit as the aliphatic portion. To our knowledge it constitutes the first example in which an isopropyl group has become detached from the terpene unit and occurs as a substituent on nitrogen. 相似文献
68.
LaChance-Galang KJ Maldonado I Gallagher ML Jian W Prock A Chacklos J Galang RD Clarke MJ 《Inorganic chemistry》2001,40(3):485-492
Pentaammineruthenium moves on ambidentate nitrogen heterocycles by both rotation and linkage isomerization, which may affect the biological activity of potential ruthenium metallopharmaceuticals. The rapid rotation rates of [(NH3)5RuIII] coordinated to the exocyclic nitrogens of isocytosine (ICyt) and 6-methylisocytosine (6MeICyt) have been determined by 1H NMR. Since these rotamers can be stabilized by hydrogen bonding between the coordinated ammines and the N1 and N3 endocyclic nitrogens, rotamerization is under pH control. Spectrophotometrically (UV-vis) measured pKa values for the two endocyclic sites for the ICyt complex are 2.78 and 9.98, and for 6MeICyt are 3.06 and 10.21, which are probably weighted averages for ionization from N3 and N1, respectively. Activation parameters for the rotamerizations were determined by variable-temperature NMR at pKa1 < pH < pKa2 for the complexes with (ICyt-kappa N2)-, (6MeICyt kappa N2)-, and 2AmPym kappa N2. For [(6MeICyt kappa N2)(-)-(NH3)5RuIII]2+, delta H* = 1.6 kcal/mol, delta S* = -37 cal/mol K, and Ea = 2.2 kcal/mol. Due to strong RuIII-N pi-bonding, the activation enthalpies are approximately 10 kcal lower than the expected values for the free ligands. Rotameric structure is correlated with pKa values, pH-dependent reduction potentials, and 1H NMR parameters. Linkage isomers of [(2AmPym)(NH3)5Ru]n+ are reported in which RuII is coordinated to the endocyclic nitrogen (N1) and RuIII to the exocyclic nitrogen (N2). The rate constant for the kappa N2-->kappa N1 isomerization as part of an ECE mechanism is 3.9 s-1 at pH 3. The pH dependence of the acid-catalyzed hydrolysis of [(2AmPym kappa N1)(NH3)5Ru]2+ is determined. 相似文献
69.
Dupont-Gillain CC Jacquemart I Rouxhet PG 《Colloids and surfaces. B, Biointerfaces》2005,43(3-4):179-186
In the last years, adsorbed collagen was shown to form layers with a supramolecular organization depending on the substrate surface properties and on the preparation procedure. If the concentration of collagen and the duration of adsorption are sufficient, fibrillar collagen structures are formed, corresponding to assemblies of a few molecules. This occurs more readily on hydrophobic compared to hydrophilic surfaces. This study aims at understanding the origin of such fibrillar structures and in particular at determining whether they result from the deposition of fibrils formed in solution or from the building of assemblies at the interface. Therefore, type I collagen solutions with an increasing degree of aggregation were prepared, using the “neutral-start” approach, by ageing pH 5.8 solutions at 37 °C for 15 min, 2 or 7 days. The obtained solutions were used to investigate the influence of collagen aggregation in solution on the supramolecular organization of adsorbed collagen layers, which was characterized by X-ray photoelectron spectroscopy and atomic force microscopy. Polystyrene and plasma-oxidized polystyrene were chosen as substrates for the adsorption. The size and the density of collagen fibrils at the interface decreased upon increasing the degree of aggregation of collagen in solution. This is explained by a competitive adsorption process between monomers and aggregates of the solution, turning at the advantage of the monomers. More aggregated solutions, which are thus depleted in free monomers, behave like less concentrated solutions, i.e. lead to a lower adsorbed amount and less fibril formation at the interface. This study shows that the supramolecular fibrils observed in adsorbed collagen layers, especially on hydrophobic substrates, are not formed in the solution, prior to adsorption, but are built at the interface, through the assembly of free segments of adsorbed molecules. 相似文献
70.
The title compound was prepared from 4-tert-butyl cyclohexanone in high yield by a simple three step procedure. 相似文献