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排序方式: 共有559条查询结果,搜索用时 15 毫秒
1.
Synthetic routes to BEDT-TTF derivatives bearing side chain carboxylic ester and amide groups are reported. Methyl ET-ethanoate was prepared in five steps from vinylacetic acid; amide groups were installed early in the synthesis by mixed anhydride methods before the final coupling reaction. 相似文献
2.
Katalytische Epoxidierung und 1,2‐Dihydroxylierung von Olefinen mit Bispidin‐Eisen(II)/H2O2‐Systemen
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5.
Villorbina G Roura L Camps F Joglar J Fabriàs G 《The Journal of organic chemistry》2003,68(7):2820-2829
The formation of methylenecyclopropanes by enzymatic desaturation of 11-cyclopropylundecanoic acid (1) and its disubstituted derivatives cis- and trans-3-5 has been investigated using the Delta(11) desaturase of Spodoptera littoralis as model enzyme. Gas chromatography coupled to mass spectrometry analyses of methanolyzed lipidic extracts from tissues incubated with each probe revealed that all the cyclopropyl fatty acids were transformed into the corresponding 11-cyclopropylidene acids, except for compound trans-5 (5b), which was not desaturated at C11. The formation of methylenecyclopropane 9 as the only reaction product from 1 indicates that a potential radical intermediate is too short-lived to allow rearrangement reactions. Information on the Delta(11) desaturase substrate binding domain is provided considering the cyclopropyl probes 3-5 as conformationally restricted analogues of the straight-chain substrates. 相似文献
6.
Héctor Beltrán Nahum Masó Beatriz Julian Eloisa Cordoncillo Juan B. Carda Purificación Escribano Anthony R. West 《Journal of Sol-Gel Science and Technology》2003,26(1-3):1061-1065
Lead Magnesium Niobate, Pb(Mg1/3Nb2/3)O3 (PMN), is an important relaxor ferroelectric material. A significant problem exists, however, in the preparation of this material: it is very difficult to prepare pure phase, without the presence of a pyrochlore impurity phase which degrades the dielectric properties. Depending on the processing conditions, the amount of pyrochlore phase varies.Considering the ternary diagram PbO-MgO-Nb2O5, different compositions have been prepared by a simple sol-gel method at room temperature using Pb(CH3COO)2, Mg(CH3COO)2, Nb(OC2H5)5 as precursors. After the heat treatment, the samples obtained were analyzed by XRD and EPMA with the purpose of studying the compositions formed.From the analysis of these results, it seems to be that the appearance of pyrochlore can be related to the reactivity of the MgO and/or the presence of other phases of the binary system PbO-Nb2O5. An excess of Pb and Mg is necessary for compositions to be formed near the PMN. The control of the amount of these two elements is very important because an excess of MgO would lead to rich compositions in Mg as a secondary phase. 相似文献
7.
García Ruano JL Fraile A González G Martín MR Clemente FR Gordillo R 《The Journal of organic chemistry》2003,68(17):6522-6534
The addition of diazomethane and diazoethane to (5S,SS)- and (5R,SS)-5-ethoxy-3-p-tolylsulfinylfuran-2(5H)-ones (1a and 1b) and their 4-methylderivatives (2a and 2b) proceeded in almost quantitative yields and complete regioselectivity. The observed pi-facial selectivity is determined by the configurations at both C-5 and the sulfinyl group, the later being the most important. The syn adducts were almost exclusively obtained from 1a and 2a in apolar solvents but the pi-facial selectivity was strongly decreased in more polar solvents. On the other hand, the major adducts from 1b and 2b were the anti ones and such predominance was slightly increased with solvent polarity. The exo-selectivity was complete in all the cases except for the anti approach to compounds 2a (in polar solvents) and 2b. The role of the sulfinyl group in this behavior was inferred by comparison of these results with those obtained in reactions of diazoalkanes with 5-methoxyfuran-2(5H)-one (3). Steric interactions seem to be the main ones responsible for the observed exo selectivity of reactions with diazoethane, but electronic factors, which can be modulated by the solvent, are also significant in the pi-facial selectivity control. DFT computational methods are able to correctly predict the reactivity, regioselectivity, and pi-facial selectivity exhibited by 5-alkoxyfuranones as well as their changes with the solvent polarity. A C-H.O hydrogen bond, involving the oxygen atom of the 5-alkoxy group at dipolarophiles and the endo-hydrogen atom at dipoles, seems to play a key role in the electronic interactions influencing the stereochemical course of these reactions. 相似文献
8.
Nikhil M. Kriplani David P. Nackashi Christian J. Amsinck Neil H. Di Spigna Michael B. Steer Paul D. Franzon Ramon L. Rick Gemma C. Solomon Jeffrey R. Reimers 《Chemical physics》2006
Two efficient, physically based models for the real-time simulation of molecular device characteristics of single molecules are developed. These models assume that through-molecule tunnelling creates a steady-state Lorentzian distribution of excess electron density on the molecule and provides for smooth transitions for the electronic degrees of freedom between the tunnelling, molecular-excitation, and charge-hopping transport regimes. They are implemented in the fREEDA™ transient circuit simulator to allow for the full integration of nanoscopic molecular devices in standard packages that simulate entire devices including CMOS circuitry. Methods are presented to estimate the parameters used in the models via either direct experimental measurement or density-functional calculations. The models require 6–8 orders of magnitude less computer time than do full a priori simulations of the properties of molecular components. Consequently, molecular components can be efficiently implemented in circuit simulators. The molecular-component models are tested by comparison with experimental results reported for 1,4-benzenedithiol. 相似文献
9.
Aguado GP Moglioni AG García-Expósito E Branchadell V Ortuño RM 《The Journal of organic chemistry》2004,69(23):7971-7978
The hydrogenation reactions of several cyclobutyl enamides derived from (-)-alpha-pinene or (-)-verbenone have been investigated by using different catalysts. The chiralities of both the substrate and the catalyst as well as the Z/E stereochemistry of the double bond have been considered, and the observed diastereoselectivity has been rationalized. For enamides with the double bond separated from the cyclobutane by a methylene, the Wilkinson catalyst did not induce any diastereoselection, but excellent diastereoselectivity was observed when using Et-DuPHOS-Rh and ChiraPHOS-Rh. The configuration of the new stereogenic center was catalyst-dependent and can be rationalized according to the Halpern mechanism. For (Z)-enamides with the double bond directly linked to the cyclobutane ring, the chirality of the substrate governed the diastereoselection and the Halpern mechanism seemed not to be operative in the hydrogenation with ChiraPHOS, with the configuration of the new stereogenic center being determined by steric effects. On the contrary, the chirality of the catalyst was the factor determining the stereochemistry of the major products with alkyl-DuPHOS-Rh. Z/E stereochemistry influenced the stereodifferentiation, and a different behavior for each Z or E stereoisomer was found. For both (Z)- and (E)-enamides, some instances of match/mismatch between the chirality of the substrate and that of the catalyst were observed. As a result of all of these studies, a series of new cyclobutyl alpha-amino acids has been synthesized. These products are interesting to incorporate into conformationally constrained peptides. 相似文献
10.
Masár M Kaniansky D Bodor R Jöhnck M Stanislawski B 《Journal of chromatography. A》2001,916(1-2):167-174
Isotachophoretic (ITP) separation and determination of a group of 13 organic and inorganic acids, currently present in wines, on a poly(methyl methacrylate) chip provided with on-column conductivity detection was a subject of a detailed study performed in this work. Experiments with the ITP electrolyte systems proposed to the separation of anionic constituents present in wine revealed that their separation at a low pH (2.9) provides the best results in terms of the resolution. Using a 94 mm long separation channel of the chip, the acids could be resolved within 10-15 min also in instances when their concentrations corresponded to those at which they typically occur in wines. A procedure suitable to the ITP determination of organic acids responsible for some important organoleptic characteristics of wines (tartaric, lactic, malic and citric acids) was developed. Concentrations of 2-10 mg/l of these acids represented their limits of quantitation for a 0.9 microl volume sample loop on the chip. A maximum sample load on the chip, under the preferred separating conditions, was set by the resolution of malate and citrate. A complete resolution of these constituents in wine samples was reached when their molar concentration ratio was 20:1 or less. ITP analyses of a large series of model and wine samples on the chip showed that qualitative indices [RSH (relative step height) values] of the acids, based on the response of the conductivity detector, reproduced with RSD better than 2% while reproducibilities of the determination of the acids of our interest characterized RSD values better than 3.5%. 相似文献