Search results for "Base"
showing 10 items of 8362 documents
Deprotonation of Fluoro Aromatics Using Lithium Magnesates.
2004
Abstract 3-Fluoropyridine was deprotonated on treatment with 1/3 equiv of Bu 3 MgLi in THF at −10 °C. The lithium arylmagnesate formed was either trapped with electrophiles or involved in a palladium-catalyzed cross-coupling reaction with 2-bromopyridine. The use of a less nucleophilic lithium-magnesium-dialkylamide, (TMP) 3 MgLi, allowed the reaction of 3-fluoroquinoline, giving the 2,2′-dimeric derivative. 2-Fluoropyridine and 2,6-difluoropyridine were deprotonated using 1/3 equiv of the highly coordinated magnesate Bu 4 MgLi 2 in THF at −10 °C in the presence of a substoichiometric amount of 2,2,6,6-tetramethylpiperidine. 1,3-Difluorobenzene reacted similarly when treated with Bu 3 MgLi;…
Aminoalkylbis(phenolate) [O,N,O] donor ligands for uranyl(VI) ion coordination: Syntheses, structures, and extraction studies
2007
Abstract The syntheses of five new aminoalkylbis(phenolate) ligands (as hydrochlorides) and their uranyl complexes are described. The reaction between uranyl nitrate hexahydrate and phenolic ligand [(N,N-bis(2-hydroxy-5-tert-butyl-3-methylbenzyl)-1-aminopropane) · HCl], H2L1 · HCl, forms a uranyl complex [UO2(HL1)2] · 2CH3CN (1). The ligand [(N,N-bis(2-hydroxy-5-tert-butyl-3-methylbenzyl)-1-aminobutane) · HCl], H2L2 · HCl, forms a uranyl complex with a formula [UO2(HL2)2] · 2CH3CN (2). The ligand [(N,N-bis(2-hydroxy-5-tert-butyl-3-methyl benzyl)-1-aminohexane) · HCl], H2L3 · HCl, yields a uranyl complex with a formula [UO2(HL3)2] · 2CH3CN (3) and the ligand [(N,N-bis(2-hydroxy-5-tert-butyl-…
Uranyl(VI) complexes with a diaminobisphenol from eugenol and N-(2-aminoethyl)morpholine: Syntheses, structures and extraction studies
2011
Abstract The syntheses and structural studies of an [O,N,O,N′]-type phenolic ligand [(N’,N’-bis(2-hydroxy-3-methoxy-5-(propen-2-yl)benzyl)-N-(2-aminoethyl)morpholine), (H2L) and two new uranyl complexes of this ligand are described. The reaction between uranyl nitrate hexahydrate and H2L in a 1:2 M ratio (M to H2L) results in a uranyl complex of the formula [UO2(HL)(NO3)(H2O)] (1). In the presence of a base (triethylamine), with the same molar ratio, the uranyl complex [UO2(HL)2]·2CH3CN (2) is formed. The molecular structures H2L, 1 and 2 were verified by X-ray crystallography. Both uranyl complexes are zwitterions with a neutral net charge. A comprehensive NMR-structural analyses of all co…
Green conditions for the Suzuki reaction using microwave irradiation and a new HNT-supported ionic liquid-like phase (HNT-SILLP) catalyst
2014
A new catalytic system based on modified halloysite nanotubes was employed in the Suzuki reaction under microwave irradiation. A set of solvents, times and bases was screened and the best experimental conditions were obtained when the reactions were carried out for 10 min in water–ethanol at 120 °C in presence of K2CO3 as base. Good recyclability was observed. The new catalytic system was employed using either 1 mol% or 0.1 mol%. The palladium catalyst displayed good activity, allowing the synthesis of several biphenyl compounds in high yield working with only 0.1 mol% palladium loading. The application of microwave irradiation decreased the reaction time and also improved conversion with r…
From ceria nanotubes to nanowires through electrogeneration of base
2009
The preparation of Ce(OH)3/CeO2 nanostructures (NSs) through electrogeneration of base into anodic alumina membranes was studied. The effects of solvent (alcohol and/or water), Ce3? partner anion nature (chloride or nitrate) and concentration, applied potential or current density in driving the morphology toward nanowires (NWs) and/or nanotubes (NTs) was described. The structural analysis performed by X-Ray Diffraction and Raman Spectroscopy allowed to evidence that the presence of Ce(IV) into the nanostructures strongly depends on the oxygen content in the growing environment.
A chalcone-based highly selective and sensitive chromofluorogenic probe for trivalent metal cations
2015
[EN] Anew chalcone-based probe for the chromofluorogenic sens-ing of trivalent (Al3 +,Fe3+,Cr3+,Ga3+,In3+and As3 +)overmono-and divalent cationsand anionsisreported. In the presence of trivalent metal cations,the probe was able to displayaremarkable color change from yellow to colorless that wasclearly visible to the naked eye. Also, the initial strongyellowemission was gradually quenched and substituted by aweaklyshifted band.
Catalytic Diastereo- and Enantioselective Synthesis of 2-Imidazolinones.
2019
Chiral cyclic ureas (2-imidazolinones) were prepared by the reaction of nitrones and isocyanoacetate esters using a multicatalytic system that combines a bifunctional Brønsted base-squaramide organocatalyst and Ag+ as a Lewis acid. The reaction could be achieved with a range of nitrones derived from aryl- and cycloalkylaldehydes with moderate diastereo- and good enantioselectivity. A plausible mechanism involving an initial formal [3 + 3] cycloaddition of the nitrone and isocyanoacetate ester, followed by rearrangement to an aminoisocyanate and cyclization to the imidazolinone, is proposed.
DNA nucleobase properties and photoreactivity: Modeling environmental effects
2009
Abstract The accurate ab initio quantum chemical (QM) method multiconfigurational second-order perturbation (CASSPT2)/complete active space self-consistent field (CASSCF) has been used in conjunction with molecular mechanics (MM) procedures to compute molecular properties and photoinduced reactivity of DNA/RNA nucleobases (NABs) in isolation and within a realistic environment, in which the double helix strand, the aqueous media, and the external counterions are included. It is illustrated that the use of an MM model is helpful both to account for short- and long-range effects of the system surrounding the QM molecular core and to provide the proper structural constraints that allow more acc…
Counterion's Effect on the Catalytic Activity of Zn-Prolinamide Complexes in Aldol Condensations
2012
The catalytic activity of complexes involving organic ligands and Lewis acids can be modulated by changing any of their components. In this work we have studied the influence on the stereoselectivity and catalytic activity exerted by the counterion of zinc salts employed as cocatalysts of L-prolinamide in aldol condensations. The structures of the complexes have been determined both in solution and in the solid state.
Lewis Acid Induced [2+2] Cycloadditions of Silyl Enol Ethers with α,β-Unsaturated Esters: A DFT Analysis
2005
The Lewis acid (LA) induced cycloaddition of trimethysilyl vinyl ether with methyl acrylate has been studied by DFT methods at the B3LYP/6-31G* level. In the absence of an LA, a [4+2] cycloaddition between the silyl enol ether and methyl acrylate in the s-cis conformation takes place through an asynchronous, concerted bond-formation process. This cycloaddition presents a large activation enthalpy of 21.1 kcal mol–1. Coordination of the LA AlCl3 to the carbonyl oxygen atom of methyl acrylate yields a change of molecular mechanism from a concerted to a two-step mechanism and produces a drastic reduction of the activation energy. This stepwise mechanism is initialized by the nucleophilic attac…