Search results for "stereo"

Aminosäureester als chirale Hilfsgruppen bei Barbier-Reaktionen in wäßriger Lösung

1991

Amino Acid Esters as Chiral Auxiliaries in Barbier-Type Reactions in Aqueous Solution Valine and proline benzyl ester are converted into the aliphatic and aromatic α-oxo amides 5 by activation of the respective α-oxo acid by means of N,N′-diisopropylcarbodiimide. The α-oxo amides 5 undergo Barbier-type reactions with differently substituted allyl halides in the presence of zinc and pyridinium toluenesulfonate in water/THF (2:1, v/v) at 4°C. Thereby, the α-hydroxy amides 8/9 are formed in high yields and, in the case of the proline ester amides, with diastereomer ratios of 4–6:1. In the absence of any allyl halide, or if the addition of the allyl moiety to the carbonyl groups is only slow, t…

VIOLURATO COMPLEXES OF Cr(III). SYNTHESIS AND CHARACTERIZATION. PROTONATION-DEPROTONATION EQUILIBRIA OF THE COORDINATED LIGANDS. EVIDENCE OF THE COOR…

1982

Abstract The formation of violurato complexes of Cr(III) has been studied in aqueous solution. Two compounds, [Cr(H2V)3].5H2O and Na[Cr(H2V)2(OH)2].4H2O have been synthesized and characterized. [Cr(H2V)3] behaves in aqueous solution as a triprotic acid but it can also add a proton yielding [Cr(H2V)2(H3V)]+. The acidity constants of this species have been determined: pKa1 =3.32, pKa2 =4.25, pKa3 =4.83 and pKa4 =6.99 (25°C, 0.1 M NaC1O4). [Cr(H2V)2(OH)2]− undergoes a deprotonation of the two H2V− ligands and a protonation of the hydroxo ligands. The acidity constants of [Cr(H2V)2(H2O)2]+ have been also determined: pKa1 =3.5, pKa2 =4.6, pKa3 =7.1 and pKa4 =9.2 (25°C, 0.1 M NaC1O4). The coordin…

Novel pathways for the preparation of mesoporous MCM-41 materials: control of porosity and morphology

1999

Two novel synthesis routes for the preparation of mesoporous MCM-41 materials are introduced. Both methods use tetra-n-alkoxysilanes such as tetraethoxysilane (TEOS) or tetra-n-propoxysilane (TPS) as a silica source which are added to an aqueous solution of a cationic surfactant in the presence of ammonia as catalyst. In this study, n-alkyltrimethylammonium bromides and n-alkylpyridinium chlorides were employed as templates. The addition of an alcohol (e.g. ethanol or isopropanol) leads to a homogeneous system which allows the formation of spherical MCM-41 particles. The main advantages of these methods are short reaction times, excellent reproducibility and easy preparation of large batche…

The influence of ultrasound on the RuI3-catalyzed oxidation of phenol: Catalyst study and experimental design

2009

Abstract The influence of ultrasound at 24 kHz on the heterogeneous aqueous oxidation of phenol over RuI3 with hydrogen peroxide (H2O2) was studied isothermally at 298 K. Effect of ultrasound irradiation on catalytic properties and performance of RuI3 has been studied in details by means of scanning electron microscopy (SEM), X-ray powder diffraction (XRD), dispersion analyzer and a surface analyzer. Turn over frequency of the catalyst was also calculated. In this work, experimental design methodology was applied to optimize the degradation of phenol in aqueous solution, while minimizing an excessive consumption of chemical reagents. The independent variables considered were the catalyst lo…

Conformational investigations of bis(α-aminoalkyl)phosphinic acids and studies of the stability of their complexes with Cu(II)

2008

Abstract Conformational investigations of a group of bis(α-aminoalkyl)phosphinic acids were performed by use of NMR spectroscopy and theoretical calculations. In the case of one of the studied compounds, substituted with aminobenzyl and amino(p-chlorobenzyl) moieties, a pH-dependent equilibrium between conformers, stabilized by intermolecular hydrogen bonds was observed. Potentiometric studies proved that these molecules formed stable complexes with copper(II) ions, where stoichiometry was 1:1 and 1:2 depending on pH of their aqueous solution.

Ellipsometric and fluorescence microscopic investigations of a cyclam derivative at the air/water interface

1993

Antivirale Wirkstoffe, 20. Mitt. 4,6-Dialkylierte 2-Benzylthiopyrimidine

1981

Aus der Kondensation von Benzylisothioharnstoff (1) mit den β-Diketonen 2a–c gehen die 2-Benzylthiopyrimidine 3a–c hervor. Wird die Reaktion 1+2b jedoch in 30proz. wasr. Kaliumcarbonat-Losung/Ethanol/Ether durchgefuhrt, so tritt unter Ethanolyse Bildung von 2-Ethoxy-4,6-diethylpyrimidin (4) ein. 2-Benzylthio-4-ethyl-6-(trifluormethyl)pyrimidin ubt Hemmwirkung gegen Influenza A-Virus aus. Antiviral Agents, XX: 4,6-Dialkylated 2-Benzylthiopyrimidines Condensations of benzylisothiourea (1) with the β-diketones 2a–c yield the 4,6-dialkylated 2-benzylthiopyrimidines 3a–c. However, in 30% aqueous potassium carbonate solution/ethanol/ether, the reaction 1+2b proceeds by ethanolysis to form 2-ethox…

A DFT Study of the Conversion of Ptaquiloside, a Bracken Fern Carcinogen, to Pterosin B in Neutral and Acidic Aqueous Medium

2017

The conversion of ptaquiloside (PtQ), a bracken fern (Pteridium aquilinum) carcinogen, to pterosin B (PtB), which is involved in the underlying mechanisms of PtQ genotoxicity and carcinogenicity, has been theoretically studied in aqueous neutral (AN) and acid (AA) media, using DFT methods at the PCM(water)-B3LYP/6-31G(d)//B3LYP/6-31G(d) computational level. The β-elimination of glucose in AN and four reactive channels (A-D) defined by as many protonation sites in PtQ were calculated. Activation enthalpy decreases (from 42.0 to 12.6 kcal mol−1) in AA relative to AN suggesting protic catalysis. The most favoured channel A started with protonation of the tertiary O15 hydroxyl of PtQ and SN1 wa…

Rinascimento alla francese: Gabriele Licciardo, architettura e costruzione nel Salento della metà del Cinquecento

2015

L’architettura salentina del XVI secolo offre ricchezza e profondità di riferimenti ma anche ostacoli posti contestualmente da una documentazione incompleta e priva di riscontri sicuri. Di questa labilità di assunti è intrisa la vicenda della personalità che viene considerata risolutiva, quella più nota per la storiografia architettonica: Gabriele Licciardo. Questo studio parte da una ricostruzione plausibile della biografia del maestro alla luce delle poche notizie esistenti e dell’architettura costruita. Per individuare aspetti utili ad inquadrare il caso Licciardo occorre osservare fabbriche note del Salento e che sono accomunate da sperimentazioni significative nel campo delle volte in …

Unusual oleanane-type saponins from Arenaria montana

2010

Three oleanane-type saponins, 3-O-β-d-glucopyranosylechinocystic acid 28-O-β-d-xylopyranosyl-(1→4)-[α-l-rhamnopyranosyl-(1→2)]-α-l-rhamnopyranosyl ester (1), 3-O-β-d-glucopyranosylechinocystic acid 28-O-α-l-arabinopyranosyl-(1→3)-β-d-xylopyranosyl-(1→4)-[α-l-rhamnopyranosyl-(1→2)]-α-l-rhamnopyranosyl ester (2), 3-O-β-d-glucopyranosylcaulophyllogenin 28-O-β-d-apiofuranosyl-(1→3)-β-d-xylopyranosyl-(1→4)-[β-d-apiofuranosyl-(1→3)]-α-l-rhamnopyranosyl-(1→2)-α-l-rhamnopyranosyl ester (3) were isolated from the whole plant of Arenaria montana. Their unusual structures for the Caryophyllaceae family were established mainly by 2D NMR techniques and mass spectrometry.