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101.
This paper describes the synthesis of a bicyclic beta-amino acid scaffold in both pure enantiomeric forms and its application as chiral auxiliary in an intramolecular version of the Ugi multicomponent reaction (U-5C-4CR) to prepare alpha-amino acid derivatives of both D- and L-series in a straightforward and very stereoselective manner. The mild conditions required for the Ugi condensation and for the removal of the chiral auxiliary make this method very attractive to prepare a wide range of differently structured N-alkylated and unalkylated amino acid derivatives. 相似文献
102.
α-acyloxyaminoamides can be prepared, with yields ranging from fair to very good (up to 89%), through an Ugi four component reaction by mixing a carbonyl component, a carboxylic acid, an isocyanide and an N-alkylated hydroxylamine in methanol. Preformed nitrones furnish the same final compounds with comparable yields. 相似文献
103.
Dyke JM Levita G Morris A Ogden JS Dias AA Algarra M Santos JP Costa ML Rodrigues P Andrade MM Barros MT 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(5):1665-1676
The thermal decompositions of methyl azidoformate (N3COOMe), ethyl azidoformate (N3COOEt) and 2-azido-N,N-dimethylacetamide (N3CH2CONMe2) have been studied by matrix isolation infrared spectroscopy and real-time ultraviolet photoelectron spectroscopy. N2 appears as an initial pyrolysis product in all systems, and the principal interest lies in the fate of the accompanying organic fragment. For methyl azidoformate, four accompanying products were observed: HNCO, H2CO, CH2NH and CO2, and these are believed to arise as a result of two competing decomposition routes of a four-membered cyclic intermediate. Ethyl azidoformate pyrolysis yields four corresponding products: HNCO, MeCHO, MeCHNH and CO2, together with the five-membered-ring compound 2-oxazolidone. In contrast, the initial pyrolysis of 2-azido-N,N-dimethyl acetamide, yields the novel imine intermediate Me2NCOCH=NH, which subsequently decomposes into dimethyl formamide (HCONMe2), CO, Me2NH and HCN. This intermediate was detected by matrix isolation IR spectroscopy, and its identity confirmed both by a molecular orbital calculation of its IR spectrum, and by the temperature dependence and distribution of products in the PES and IR studies. Mechanisms are proposed for the formation and decomposition of all the products observed in these three systems, based on the experimental evidence and the results of supporting molecular orbital calculations. 相似文献
104.
Comprehensive two-dimensional liquid chromatography-size-exclusion chromatography (LC x SEC) was investigated as a tool for the characterization of functional poly(methyl methacrylate) (PMMA) polymers. Ultraviolet-absorbance and evaporative light-scattering detection (ELSD) were used. A simple method to quantify ELSD data is presented. Each data point from the ELSD chromatogram can be converted into a mass concentration using experimental calibration curves. The qualitative and quantitative information obtained on two representative samples is used to demonstrate the applicability of LC x SEC for determining the mutually dependent molar-mass distributions (MMD) and functionality-type distributions (FTD) of functional polymers. The influence of the molar mass on the retention behavior in LC was investigated using LC x SEC for hydroxyl-functional PMMA polymers. The critical conditions, at which retention is--by definition--independent of molar mass, were not exactly the same for PMMA series with different end-groups. Our observations are in close agreement with theoretical curves reported in the literature. However, for practical applications of LC x SEC it is not strictly necessary to work at the exact critical solvent composition. Near-critical conditions are often sufficient to determine the mutually dependent distributions (MMD and FTD) of functional polymers. 相似文献
105.
Both cis- and trans-N-benzyl-azetidine-2,4-dimethanols5 and 6 were prepared and submitted to acetylation in organic solvents catalyzed by lipases. Asymmetrization of diol 5 gave ohe corresponding monoacetate 7, while double sequential kinetic resolution of reacemic 6 gave optically enriched diol 6b and its enantiomer as the corresponding diacetate 10a. Optimized reaction conditions furnished 7, 6b and 10a with e.e. > 99%. 相似文献
106.
Michelin SE Oliveira HL Kroin T Soares LS Veiteinheimer E Luz CA Lima MF Fujimoto MM Lee MT 《The Journal of chemical physics》2005,122(9):094309
In this work, we present a theoretical study on elastic electron collisions from three isoelectronic free radicals (CNN, NCN, and CCO) in the low incident energy range. More specifically, calculated differential, integral, and momentum transfer cross sections are reported in the 1-30 eV energy range. Calculations are performed in the static-exchange and static-exchange-polarization levels. The iterative Schwinger variational method is used to solve the scattering equations. Our study reveals that the calculated cross sections for the three targets are significantly different at incident energies below 10 eV. Above that energy, a remarkable similarity among the calculated results is seen. 相似文献
107.
Rodrigues e Silva AA da Silva Góes AJ de Lima WT de Souza Maia MB 《Chemical & pharmaceutical bulletin》2003,51(12):1351-1355
The search for new anti-inflammatory drugs has been constant in several research centers. The use of the Bioisostery concept allows the elaboration of new bioactive compounds with different properties through the introduction of substitute groups in one or more positions of a main molecule with known biological activity. Preliminary works accomplished at our laboratory with 2,4-thiazolidinedione isosters demonstrated inhibitory activity on edema formation for N-tryptophyl-5-(3,5-di-tert-butyl-4-hydroxybenzylidene)-2,4-thiazolidinedione (GS28) and N-tryptophyl-5-(3,5-di-tert-butyl-4-hydroxybenzylidene) rhodanine (GS26). We verified the antiedematogenic and ulcerogenic activity of these two compounds in Wistar rats. The carrageenan induced paw edema suffered significant (p<0.05) inhibition (28.36% on average) for GS28 (100 mg/kg; v.o.) during the entire time of the experiment. GS26 (50 and 100 mg/kg; v.o.) significantly inhibited (p<0.05) the paw edema dextran induced (22.1 and 27.8%, for the respective doses) after 180 min. The compounds GS26 and GS28 did not show ulcerogenic activity on gastric mucous. The results suggest antiedematogenic action for both compounds without the appearance of gastric lesions. 相似文献
108.
Anna Rakowska Robert Filipek Krzysztof Sikorski Marek Danielewski Renata Bachorczyk 《Mikrochimica acta》2004,145(1-4):183-186
The interdiffusion process in thin and thick (500nm–60µm) Au–Ni layers deposited on different substrates is studied using the EDS technique. In-depth X-ray analysis based on the Pouchou and Pichoir method is applied for obtaining the concentration profiles in nanometre scale multi-layers. A theoretical analysis using the Darken method is employed for modelling interdiffusion in the Au–Ni system. Computer simulations, where intrinsic diffusivities of the Au and Ni are functions of composition, are presented and compared with experimental results. 相似文献
109.
Jose′ L. F. C. Lima Antoacutenio O. S. S. Rangel M. Renata S. Souto 《Fresenius' Journal of Analytical Chemistry》1997,358(5):657-662
A flow injection system was developed for the sequential determination of total nitrogen and phosphorus in digests of vegetables
using potentiometric and spectrophotometric detection systems, respectively. A tubular ammonium selective electrode with a
sensor system composed of nonactin/monactin in tris(2-ethylhexyl) phosphate was used. The selectivity limitations of this
electrode were overcome by the inclusion of a gas-diffusion unit in the system that separated ammonium from the rest of the
sample matrix and allowed the determination of total nitrogen and phosphorus by the partition of the sample plug between two
streams.
The results obtained with the developed FIA system were in good agreement with those of the reference methods. Sampling rates
from 40 to 60 samples per hour and relative standard deviations below 3.5% were achieved.
Received: 17 October 1996/Revised: 21 November 1996/Accepted: 27 November 1996 相似文献
110.
Inductively coupled plasma optical emission spectrometry (ICP-OES) was applied to the analysis of major and minor elements of Ni-Nb alloys obtained by aluminothermic reduction process. Digestion of samples was made using a mixture of HF+HNO3. Minor and trace elements were determined without matrix separation. The precision for all constituents was <3%. Recoveries for the analyte-spiked samples were 95%. 相似文献