868 resultados para Reactions in Polar Aprotic Media


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A rapid one-pot synthesis of 3-alkyl-5-[(Z)-arylme­thylidene]-1,3-thiazolidine-2,4-dionesis described that occurs in recyclable ionic liquid [bmim]PF6 (1-butyl-3-methylimidazolium hexafluorophosphate).Significant rate enhancement and good selectivity have been observed.

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The room temperature ionic liquid N-butylpyridinium tetrafluoroborate, [bpy]BF4 is used as a "green" recyclable alternative to classical molecular solvents for the alkylation of Meldrum's acid.

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The moisture and air stable ionic liquids 1-butyl-3-methylimidazonium tetrafluoroborate [bmim]BF4 and 1-butyl-3-methylimidazonium hexafluorophosphate [bmim]PF6 were used as ‘green' recyclable alternatives to volatile organic solvents (VOCs) for ethylenediammonium diacetate (EDDA) catalyzed Knoevenagel condensation between aldehydes or ketones with active methylene compounds. Both aldehydes and ketones gave satisfactory results. The ionic liquids containing catalyst EDDA were recycled several times with no decreases in yields and reaction rates. In the case of 2-hydroxybenzaldehyde, the reactions led to the formation of 3-substituted coumarins under standard reaction conditions.

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The room temperature ionic liquid, n-butylpyridinium tetrafluoroborate (BPyBF4) is used as a "green" recyclable alternative to classical molecular solvents for the a-tosyloxylation of ketones.

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The room temperature ionic liquid it-butylpyridinium tetrafluoroborate (BPyBF4) is used as a `green' recyclable alternative to classical molecular solvents for the cyclocondensation of alpha-tosyloxyketones with 2-aminopyridine. Significant rate enhancements and improved yields have been observed.

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Three British bituminous coals, (Gedling, Cresswell, and Cortonwood Silkstone) were selected for study. Procedures were developed, using phase transfer catalysts (PTC's), to degrade the solvent insoluble fractions of the coals. PTC's are of interest because they have the potential to bring about selective high conversion reactions, under mild conditions, (often in the past, severe reaction conditions have had to be used to degrade the coals, this in turn resulted in the loss of much of the structural information). We have applied a variety of physical and chemical techniques to maximise the amount of structural information, these include, elemental analysis, 1H-NMR, 13C-CPMAS-NMR, GPC, GC-MS, FTIR spectroscopy, DRIFT spectroscopy, and gas adsorption measurements. The main conclusions from the work are listed below:- ( 1 ) PTC O-methylation; This reaction removes hydrogen bonds within the coal matrix by 'capping' the phenolic groups. It was found that the polymer-like matrix could be made more flexible, but not significantly more soluble, by O-methylation. I.E. the trapped or 'mobile' phase of the coals could be removed at a faster rate after this reaction had been carried out. ( 2 ) PTC Reductive and Acidic Ether Cleavage; The three coals were found to contain insignificant amounts of dialkyl and alkyl aryl ethers. The number of diaryl ethers could not be estimated, by reductive ether cleavage, (even though a high proportion of all three coals was solublised). The majority of the ethers present in the coals were inert to both cleavage methods, and are therefore assumed to be heterocyclic ethers. ( 3 ) Trif!uoroperacetic Acid Oxidation; This oxidant was used to study the aliphatic portions of the polymer-like macromolecular matrix of the coals. Normally this reagent will only solublise low rank coals, we however have developed a method whereby trifluoroperacetic acid can be used to degrade high rank bituminous coals. ( 4 ) PTC/Permanganate Oxidation; This reagent has been found to be much more selective than the traditional alkaline permanganate oxidation, with a lot more structural information being retained within the various fractions. This degradative method therefore has the potential of yielding new information about the molecular structure of coals.

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The binding of iron (59Fe) and gallium (67Ga) to the plasma protein transferrin (Tf) was investigated by G75 gel filtration chromatography in control patients and treated and untreated patients with Parkinson's disease (PD). Fe-Tf binding was 100% in all controls and PD patients suggesting that a defect in Fe-Tf binding was not involved in the aetiology of PD. Ga-Tf binding was significantly reduced in both untreated and treated PD patients compared to controls. In addition, treated PD patients had significantly higher Ga-Tf binding than untreated patients. A reduction in metal binding to Tf could result in the increase of a low molecular weight species which may more readily enter the CNS. Alternatively, it could lead to a decrease in the transport of essential metals into the brain via the Tf receptor system. A significant elevation in neopterin was demonstrated within the plasma of untreated PD patients compared to controls suggesting the activation of a cellular immune response. Furthermore, plasma neopterin was lower in treated compared to untreated PD patients, although the difference was not significant. There was no evidence for the activation of the humoral immune response in untreated or treated PD patients as measured by circulating immune complex (CIC) levels within the plasma. An inverse relationship between Ga-Tf binding and neopterin was observed in untreated PD patients. The addition of oxidants in the form of potassium permanganate and activated manganese dioxide reduced Ga-Tf binding in control plasma. However, relatively little response was observed using monocyte preparations. The results suggest that oxidants produced by activation of the cellular immune system could damage the Tf molecule thereby reducing its ability to bind metals.

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A novel kind of Airy-based pulse with an invariant propagation in lossy dispersive media is proposed. The basic principle is based on an optical energy trade-off between different parts of the pulse caused by the chromatic dispersion, which is used to compensate the attenuation losses of the propagation medium. Although the ideal concept of the proposed pulses implies infinite pulse energy, the numerical simulations show that practical finite energy pulses can be designed to obtain a partially invariant propagation over a finite distance of propagation.

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A continuous multi-step synthesis of 1,2-diphenylethane was performed sequentially in a structured compact reactor. This process involved a Heck C-C coupling reaction followed by the addition of hydrogen to perform reduction of the intermediate obtained in the first step. Both of the reactions were catalysed by microspherical carbon-supported Pd catalysts. Due to the integration of the micro-heat exchanger, the static mixer and the mesoscale packed-bed reaction channel, the compact reactor was proven to be an intensified tool for promoting the reactions. In comparison with the batch reactor, this flow process in the compact reactor was more efficient as: (i) the reaction time was significantly reduced (ca. 7 min versus several hours), (ii) no additional ligands were used and (iii) the reaction was run at lower operational pressure and temperature. Pd leached in the Heck reaction step was shown to be effectively recovered in the following hydrogenation reaction section and the catalytic activity of the system can be mostly retained by reverse flow operation. © 2009 Elsevier Inc. All rights reserved.

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A novel kind of Airy-based pulse with an invariant propagation in lossy dispersive media is proposed. The basic principle is based on an optical energy trade-off between different parts of the pulse caused by the chromatic dispersion, which is used to compensate the attenuation losses of the propagation medium. Although the ideal concept of the proposed pulses implies infinite pulse energy, the numerical simulations show that practical finite energy pulses can be designed to obtain a partially invariant propagation over a finite distance of propagation.

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We investigate the mobility of nonlinear localized modes in a generalized discrete Ginzburg-Landau-type model, describing a one-dimensional waveguide array in an active Kerr medium with intrinsic, saturable gain and damping. It is shown that exponentially localized, traveling discrete dissipative breather-solitons may exist as stable attractors supported only by intrinsic properties of the medium, i.e., in the absence of any external field or symmetry-breaking perturbations. Through an interplay by the gain and damping effects, the moving soliton may overcome the Peierls-Nabarro barrier, present in the corresponding conservative system, by self-induced time-periodic oscillations of its power (norm) and energy (Hamiltonian), yielding exponential decays to zero with different rates in the forward and backward directions. In certain parameter windows, bistability appears between fast modes with small oscillations and slower, large-oscillation modes. The velocities and the oscillation periods are typically related by lattice commensurability and exhibit period-doubling bifurcations to chaotically "walking" modes under parameter variations. If the model is augmented by intersite Kerr nonlinearity, thereby reducing the Peierls-Nabarro barrier of the conservative system, the existence regime for moving solitons increases considerably, and a richer scenario appears including Hopf bifurcations to incommensurately moving solutions and phase-locking intervals. Stable moving breathers also survive in the presence of weak disorder. © 2014 American Physical Society.

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A márkatulajdonosok számára elsődleges fontosságú, hogy feltérképezzék saját márkaközösségüket, ezáltal is elősegítve a közösségi fókuszú kommunikációs tevékenységüket. Különösen igaz ez a jellemzően kis- és középvállalati formában működő vendéglátóhelyek számára, ahol a közösségi média sokszor az egyetlen rendelkezésre álló marketingkommunikációs eszköz. Empirikus kutatásunkban fogyasztói narratívákat (n=151) elemzünk a tartalomelemzés módszertanával. A válaszadókat arra kértük, hogy írjanak kedvenc vendéglátóhelyükkel való kapcsolatukról az online térben. Elemzésünkben arra keressük a választ, hogy a márkaközösségek tagjai milyen belső indíttatásból kerültek kapcsolatba kedvenc vendéglátóhelyeikkel a közösségi platformokon. Az elsősorban fogyasztási élményekhez kötött kapcsolat online közösségi térbe való kiterjesztésére olyan belső motivációkat tártunk fel, mint a pragmatikusabb információközpontú indíttatások (pl. kizárólagos információk, naprakészség, vállalati ajánlatok, közösségimédia-specifikus tartalmakhoz való hozzáférés igénye), az érzelmi kötődés kifejezése (pl. nosztalgia, ismerősöknek való ajánlás, személyes érintettség), a társas befolyás (oldalak kedvelése mint kommunikációs tartalom, konformitás, önkifejezés), valamint a vállalati alapképességeken túlmutató egyéb tematikus kapcsolódások. ____ It is of primary importance for brand owners to map their own brand community, in order to stimulate their social-focused communication activity. This is especially true for typically small and medium-sized catering enterprises, where in most cases, social media is the only available marketing communications tool. In our empirical research, we analyze consumer narratives (n=151) with the methodology of content analysis. We asked the respondents to write about their relationship with their most preferred catering establishments in the online social sphere. In our research, we search for the inner intention by which members of brand communities got connected with their most preferred catering establishments on social platforms. We revealed such inner motivations for users extending a primarily experience (an consumption) based relationship to the online social sphere like rather pragmatic, information-focused intentions (e.g. exclusive information, timeliness, company offers, access claim for social media -specific contents), the expression of emotional binding (e.g. nostalgia, reference for acquaintances, personal involvement), social influence (the like as communication content, conformity, self-expression), and other thematic linkages beyond core company competences.