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31.
Wolfgang Stadlbauer Rita Laschober Thomas Kappe 《Monatshefte für Chemie / Chemical Monthly》1991,122(10):853-861
Summary 4-Chloro-3-aryl-coumarins and quinolones2 a–e undergo thermolytic ring closure by reaction with sodium azide in refluxing dimethyl formamide to yield indolo[3,2-c]coumarins and indolo[3,2-c]quinolin-6(5H)-ones6 a–e. In the case of the coumarin2 a the azido coumarin5 can be isolated. The mono- and diazacoumestrol-dimethylethers6 a–c are converted into the coumestrol analogues7 a–c and their diacetyl derivatives8 a–c.
Potentielle nichtsteroidale Östrogene und Antiöstrogene, 4. Mitt.: Organische Azide in der Heterocyclensynthese, Teil 13: Synthese von Aza- und Diazacumöstrolen über Azidzwischenstufen
Zusammenfassung 4-Chlor-3-arylcumarine und-chinolone2 a–e reagieren thermolytisch mit Natriumazid in siedendem Dimethylfomamid unter Ringschluß zu Indolo[3,2-c]cumarinen und Indolo[3,2-c]chinolin-6(5H)-onen6 a–e. Nur aus dem Cumarinderivat2 a kann das zwischenzeitlich gebildete Azidocumarin5 isoliert werden. Die so erhaltenen Mono- und Diazacumöstroldimethylether6 a–c werden in die entsprechenden Cumöstrole7 a–c und ihre Diacetylderivate8 a–c umgewandelt.相似文献
32.
Pinto SS Diogo HP Guedes RC Costa Cabral BJ Minas da Piedade ME Martinho Simões JA 《The journal of physical chemistry. A》2005,109(42):9700-9708
The energetics of the phenolic O-H bond in the three hydroxybenzoic acid isomers and of the intramolecular hydrogen O-H- - -O-C bond in 2-hydroxybenzoic acid, 2-OHBA, were investigated by using a combination of experimental and theoretical methods. The standard molar enthalpies of formation of monoclinic 3- and 4-hydroxybenzoic acids, at 298.15 K, were determined as Delta(f)(3-OHBA, cr) = -593.9 +/- 2.0 kJ x mol(-1) and Delta(f)(4-OHBA, cr) = -597.2 +/- 1.4 kJ x mol(-1), by combustion calorimetry. Calvet drop-sublimation calorimetric measurements on monoclinic samples of 2-, 3-, and 4-OHBA, led to the following enthalpy of sublimation values at 298.15 K: Delta(sub)(2-OHBA) = 94.4 +/- 0.4 kJ x mol(-1), Delta(sub)(3-OHBA) = 118.3 +/- 1.1 kJ x mol(-1), and Delta(sub)(4-OHBA) = 117.0 +/- 0.5 kJ x mol(-1). From the obtained Delta(f)(cr) and Delta(sub) values and the previously reported enthalpy of formation of monoclinic 2-OHBA (-591.7 +/- 1.3 kJ x mol(-1)), it was possible to derive Delta(f)(2-OHBA, g) = -497.3 +/- 1.4 kJ x mol(-1), Delta(f)(3-OHBA, g) = -475.6 +/- 2.3 kJ x mol(-1), and Delta(f)(4-OHBA, cr) = -480.2 +/- 1.5 kJ x mol(-1). These values, together with the enthalpies of isodesmic and isogyric gas-phase reactions predicted by density functional theory (B3PW91/aug-cc-pVDZ, MPW1PW91/aug-cc-pVDZ, and MPW1PW91/aug-cc-pVTZ) and the CBS-QMPW1 methods, were used to derive the enthalpies of formation of the gaseous 2-, 3-, and 4-carboxyphenoxyl radicals as (2-HOOCC(6)H(4)O(*), g) = -322.5 +/- 3.0 kJ.mol(-1) Delta(f)(3-HOOCC(6)H(4)O(*), g) = -310.0 +/- 3.0 kJ x mol(-1), and Delta(f)(4-HOOCC(6)H(4)O(*), g) = -318.2 +/- 3.0 kJ x mol(-1). The O-H bond dissociation enthalpies in 2-OHBA, 3-OHBA, and 4-OHBA were 392.8 +/- 3.3, 383.6 +/- 3.8, and 380.0 +/- 3.4 kJ x mol(-1), respectively. Finally, by using the ortho-para method, it was found that the H- - -O intramolecular hydrogen bond in the 2-carboxyphenoxyl radical is 25.7 kJ x mol(-1), which is ca. 6-9 kJ x mol(-1) above the one estimated in its parent (2-OHBA), viz. 20.2 kJ x mol(-1) (theoretical) or 17.1 +/- 2.1 kJ x mol(-1) (experimental). 相似文献
33.
Rita Patakfalvi Albert Oszk Imre D k ny 《Colloids and surfaces. A, Physicochemical and engineering aspects》2003,220(1-3):45-54
Ag nanoparticles were synthetized in the interlamellar space of a layered kaolinite clay mineral. Disaggregation of the lamellae of non-swelling kaolinite was achieved by intercalation of dimethyl sulfoxide. The kaolinite was suspended in aqueous AgNO3 solution and, after adsorption of Ag+, the ions were reduced with NaBH4. The interlamellar space limits particle growth (dave=3.8–4.2 nm); however, larger silver particles may be formed on the exterior surface of kaolinite with dave=5.6–10.5 nm diameter. The diameter of the particles prepared in this way is depending on the initial AgNO3 concentration. The silver nanoparticles prepared were characterized by UV–vis spectroscopy, X-ray diffraction (XRD), Small angle X-ray scattering (SAXS), X-ray photoelectron spectroscopy (XPS) and Transmission electron microscopy (TEM). 相似文献
34.
Estrela Rde C Salvadori MC Raices RS Suarez-Kurtz G 《Journal of mass spectrometry : JMS》2003,38(4):378-385
A method based on solid-phase extraction coupled to liquid chromatography with positive ion electrospray ionization and tandem mass spectrometric detection was developed for the determination of didanosine in human serum, using lamivudine as internal standard. The acquisition was performed in the multiple reaction monitoring mode, monitoring the transitions m/z 237 --> 136.7 for didanosine and m/z 230 --> 111.7 for lamivudine. The method was linear over the range studied (10-1500 ng ml(-1)), with r(2) > 0.98, and the run time was 5 min. The intra- and inter-assay precisions were < or =10% and the intra- and inter-assay accuracies were >95%. The absolute recoveries were 99.8% (10 ng ml(-1)), 98.4% (30 ng ml(-1)), 91.5% (700 ng ml(-1)) and 94.7% (1200 ng ml(-1)). The limits of detection and quantitation were 5 and 10 ng ml(-1), respectively. The method was applied to a bioequivalence study, in which 24 healthy adult volunteers (12 men) received single oral doses (200 mg) of reference and test didanosine formulations (buffered powder for oral solutions), in an open, two-way, randomized, crossover protocol. The 90% confidence interval of the individual ratios (test formulation/reference formulation) for C(max) (peak serum concentration) and AUC(0-inf) (area under the serum concentration versus time curve from time zero to infinity) were within the range 80-125%, which supports the conclusion that the two formulations are bioequivalent regarding the rate and extent of didanosine absorption. 相似文献
35.
Luca Bernazzani Maria Rita Carosi Celia Duce Paolo Gianni Vincenzo Mollica 《Journal of solution chemistry》2006,35(11):1567-1585
Excess molar volumes, V
m
E, over the whole composition range for binary mixtures of 1-butanol, 2-butanol, and 2-methyl-2-propanol + 1-octanol, or 2-octanol, or di-n-butyl ether, or n-hexylacetate were determined at 298.15 K from density measurements carried out with a vibrating-tube densimeter. Small V
m
E values, both positive and negative, are displayed by mixtures containing 1- or 2-octanol, whereas positive and larger values are always found for mixtures containing dibutyl ether and hexylacetate. These results can be justified in terms of H-bonding interactions and/or steric hindrance due to the branched alkyl chains. Partial molar volumes at infinite dilution of the isomeric butanols in the C8 compounds were also calculated from the apparent molar volumes in dilute solution. The solute-solvent interactions and the effects of the local organisation of the solvent around the butanol molecules were discussed using the void and cavity volumes as different estimates of the intrinsic volume of the molecules. The volumetric behavior of butanols seems to be determined by the solute-solvent interactions rather than packaging effects. 相似文献
36.
Westman-Brinkmalm A Karlsson G Brive LM Hedberg-Fogel K Persson R Karlsson H Ekman R Blennow K 《Rapid communications in mass spectrometry : RCM》2005,19(24):3651-3658
In this study we have investigated whether micro-solution isoelectric focusing (microsol-IEF) can be used as a pre-fractionation step prior to liquid chromatography/tandem mass spectrometry (LC/MS/MS) and if extensive sample purification of the different fractions is required. We found that, in spite of the high concentrations of buffer and detergents, no clean up of the digested microsol-IEF fractions was necessary before analysis by LC/MS/MS. We also concluded that it is possible to identify at least twice as many proteins in a glioma cell lysate with the combination of microsol-IEF and LC/MS/MS than with LC/MS/MS alone. Furthermore, most of the proteins that were identified from one microsol-IEF fraction by using analytical narrow-range two-dimensional polyacrylamide gel electrophoresis (2D-PAGE) and peptide mass fingerprinting with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) were also identified by LC/MS/MS. Finally, we used the combination of microsol-IEF and LC/MS/MS to compare two sample preparation methods for glioma cells and found that several nuclear, mitochondria, and endoplasmic reticulum proteins were only present in the sample that had been subjected to lipid extraction by incubating the homogenized cells in chloroform/methanol/water. 相似文献
37.
Rita Khanna 《Pramana》1983,20(4):267-277
Using the continuum theory of linear elasticity, Huang diffuse scattering (HDS) has been calculated from self-interstitials in a general orthorhombic and tetragonal lattice. Various defect configurations are represented according to the point group symmetry of the defect site. The contribution toHDS from all possible equivalent orientations (assumed to be equally populated) of the defect configuration is averaged. The limitations ofHDS in discriminating between defect configurations having the same long-range symmetry are discussed, considering some special cases. 相似文献
38.
Santosh K. Mondal Parimal Paul Rita Roy Kamalaksha Nag 《Transition Metal Chemistry》1984,9(7):247-250
Summary Complexes of nickel(II), palladium(II), copper(II), cobalt(II), and cobalt(III) with methyl-2-(-salicylaldiminoethyl)-cyclopent-1-en-dithiocarboxylate (H2L1) and methyl-2-(-salicylaldiminoisopropyl)cyclopent-1-en-dithiocarboxylate (H2L2) have been prepared. They contain the donor sites ONNS. The metal(II) ions from neutral, monomeric square planar chelate complexes. The cobalt(III) complexes [CoL1-(H2O)2]X (X=Cl or ClO4) appear to betrans-diaqua-species. All compounds have been characterized by a number of physico-chemical methods. 相似文献
39.
A series of bissilylated arenium ions 1 with different substitution patterns on the aryl ring have been synthesized by hydride abstraction from 2-aryl-substituted 2,6-dimethyl-2,6-disilaheptanes (2) via transient silylium ions. The arenium ions have been identified by their characteristic NMR chemical shifts, (delta(29)Si=19.1-25.6, delta(13)C(ipso) =89.0-102.4, delta(13)C(ortho)=160.9-182.0, delta(13)C(meta)=132.5-146.9, delta(13)C(para)=150.2-169.9) supported by quantum mechanical calculations of structures, energies, and magnetic properties at the B3LYP/6-311G(d,p)//B3LYP/6-31G(d) + DeltaZPVE level of theory. The calculations clearly reveal the charge dispersing and stabilizing effect of the silyl substituents in arenium ions 1. The bissilylated benzenium ion 1a is more stable than the parent benzenium ion (C(6)H(7)(+)) by 37.6 kcalmol(-1). The synthesized arenium ions 1 are stable in solution at room temperature for periods ranging from a few hours to days. This unusual stability is attributed to: 1) the thermodynamic stabilization of the arenium ion by two beta-silyl substituents and 2) the essentially non-nucleophilic reaction conditions (the use of the weakly coordinating [B(C(6)F(5))(4)](-) anion and aromatic hydrocarbons as solvents). Addition of stronger nucleophiles than aromatic hydrocarbons (for example, acetonitrile) results in desilylation of the arenium ion 1 and recovery of the 2-aryl-2,6-disilaheptane moiety. 相似文献
40.
Carabias-Martínez R Rodríguez-Gonzalo E Domínguez-Alvárez J Hernández-Méndez J 《Electrophoresis》2002,23(3):494-501
The separation and determination of a mixture of chloro- and methylthiotriazines in water samples by both micellar electrokinetic capillary chromatography (MEKC) and nonaqueous capillary zone electrophoresis (NA-CZE) were compared. The characteristics of both methods proved to be very similar in terms of separation efficiency and analysis times, but application of these methods for the analysis of triazines in natural waters, with a prior preconcentration step, revealed significant differences. A preconcentration step by solid-phase extraction (SPE) with Oasis HLB cartridges was accomplished for the determination of triazines at sub-ppb levels in drinking and river waters; when NA-CZE was used after this SPE step, electropherograms with fewer interferences and more stable baselines were obtained than when separation was carried out using MEKC. Another aspect related to the application to real samples was the lack of precision encountered upon evaluating the electrophoretic signals generated when using SPE coupled with NA-CZE. Here, we demonstrate the importance of choosing an appropriate internal standard for analyte quantification. It is recommended that a triazine belonging to the same family as that of the triazine to be determined should be used as internal standard. 相似文献