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showing 10 items of 1247 documents
Reactions of Tris(ethanediolato)tungsten and Tungsten Oxytetrachloride with Aminotris(phenol)s: Alkoxide, Chloro, and Alkyl Derivatives of Oxotungst…
2005
Trisdiolatotungsten(VI) complex [W(eg)3] (eg = 1,2-ethanediolato dianion) reacts in refluxing toluene solution with phenolic ligand precursors tris(2-hydroxy-3,5-dimethylbenzyl)amine (H3LMe) and tris(2-hydroxy-3,5-di-tert-butylbenzyl)amine (H3LtBu) to form monomeric oxotungsten(VI) complexes [WO(LMe)(Heg)] and [WO(LtBu)(Heg)], respectively. These complexes undergo chloride-for-alkoxide substitution when treated with SOCl2 in CH2Cl2, which leads to the formation of corresponding chloro complexes [WO(LMe)Cl] and [WO(LtBu)Cl]. Identical chloro complexes are also formed in the reaction between these phenolic ligand precursors and [WOCl4]. The reaction of [WO(LR)Cl] complexes with Grignard reage…
Supported liquid membrane separation of amine and amino acid derivatives with chiral esters of phosphoric acids as carriers
2003
Studies on the possible use of phosphate and phosphonate esters bearing chiral menthol or nopol moieties as carriers for the transport of amines, amino acids, and amino acid esters through supported liquid membranes (SLM) are presented. Additionally, the enantioselectivity of the SLM transport of alkyl esters of aromatic amino acids and a non‐protein amino acid was also evaluated. It could be concluded that the extent of transport strongly depends on the hydrophobicity of the amino compound. Moreover, the carrier structure also influences the transport of those compounds through SLM: chiral phosphate and phosphonate esters appear to be poor or moderate carriers for enantioselective SLM tran…
STUDIEN ZUM VORGANG DER WASSERSTOFFÜBERTRAGUNG 621HERSTELLUNG UND ELEKTROREDUKTIVE SPALTUNG EINIGER ARYLDISULFONSÄUREDERIVATE
1982
Abstract Benzene-disulfonylchlorides were converted to the corresponding dialkyl-and diphenylesters, N-alkyl-and N-aryl disulfonamides. The half-wave-potentials E1/2 1 and E1/2 2 were measured and the products obtained on potentiostatic fission at E1/2 1 were isolated and characterized. The electroreduction of benzene-1,4-disulfonic acid-diphenylester in methanol yields phenol in a quantity approximately corresponding to the current passed, but no corresponding quantity of sulfinic acid. In dry acetonitrile, benzene-1,4-disulfonic acid diesters and diamides undergo potentiostatic fission (at E1/2 1) in good chemical and current yields, giving the corresponding monosulfonate-sulfinic acid or…
ChemInform Abstract: First Evidence of Proline Acting as a Bifunctional Catalyst in the Baylis-Hillman Reaction Between Alkyl Vinyl Ketones and Aryl …
2008
Proline in the presence of sodium hydrogen carbonate has been found to be an effective catalyst for the Baylis–Hillman reaction between methyl or ethyl vinyl ketone and aryl aldehydes. Screening of several amine catalysts showed that an ionizable carboxylic function directly linked to the secondary amine catalyst plays an important role in the synthesis of the desired product in good yield. The data obtained has allowed us to suggest, for the first time, that proline, sarcosine, pipecolinic acid and homoproline may act as bifunctional catalysts via a bicyclic enaminolactone species as intermediate. Quantum-mechanical calculations (PM3/COSMO and ab initio 3-21G/COSMO) support this mechanism …
Fluorous TBAF: A Convenient and Selective Reagent for Fluoride-Mediated Deprotections
2009
A fluorous analogue of TBAF has been developed for its use in the clean removal of silicon-derived protecting groups. Purification of the crude mixtures by fluorous solid-phase extractions allowed alcohols, amines, and carboxylic acids to be obtained in high purity, with no need of chromatographic separations. The moderate reactivity of fluorous TBAF was exploited in selective deprotections of several bifunctional molecules.
Synthese und13C-NMR-Spektroskopie cyclischer und acyclischer β-Phosphonioenamine
1979
Quartare Phosphoniumsalze, die auser einem Allyl- einen Alkinylrest (z. B. 1) oder einen Acylmethylrest tragen (z. B. 4–6) reagieren mit primaren Aminen zu den bisher unbekannten 1,2,3,4-Tetrahydro-1,4-azaphosphoriniumsalzen 2, 3, 8–12, 19 und 25. Die Umsetzung von 4 liefert in Abhangigkeit vom eingesetzten Amin auser 8–12 die 5-Amino-1,2,3,4-tetrahydro-3-methylphosphoriniumsalze 13–16 die im sauren Medium schnell zu 17 hydrolysieren. Als Zwischenstufen der Cyclisierung von 4 konnen die offenkettigen β-Phosphonioenamine 18, 20 und 21 isoliert werden. Die Cyclisierung von 18 zu 19 gelingt erst in Gegenwart von Triethylamin als Base. Struktur und Konfiguration der neuen Verbindungen werden mi…
An Unexpected Three-Component Condensation Leading to Amino- (3-oxo-2,3-dihydro-1H-isoindol-1-ylidene)- acetonitriles
2004
The reaction of 2-carboxybenzaldehyde with primary amines in the presence of cyanide leads to the formation of 2-substituted amino(3-oxo-2,3-dihydro-1H-isoindol-1-ylidene)acetonitriles. These compounds originate from the condensation of 2-carboxybenzaldehyde with the amine and two molecules of hydrogen cyanide and represent a novel class of isoindolinones.
Fast Response Heating Module for Temperature Programmed GC Analysis in Microreaction Systems
2000
For monitoring the reactant and product concentrations of a gas phase microreactor for ethylene oxide synthesis the development of a miniaturised device for fast GC analysis suitable for operation in conjunction with the microreactor is advantageous. Therefore, a method employing short (0.2 – 0.4 m) packed capillary columns was developed. Highly crosslinked polystyrene microspheres proved to be the most suitable adsorbent enabling a high separation efficiency. For fast temperature programming design concepts for an efficient heating module capable to be used with short capillary columns were developed. In principle, planar as well as cylindrical designs are suitable for integration of a res…
Preparation of N,O-Aminals as Synthetic Equivalents of H2C=NAr and (H2C=NHAr)+ Ions: Neutral and Acid-promoted Transformations
1988
A general method for the synthesis of N,O-aminals derived from primary aromatic amines is described. The reactivity of these compounds under neutral and acidic conditions has been studied and the title compounds can be envisaged as general purpose H2C=NAr or (H2C=NHAr)+ equivalents. N,O-Aminals have been converted into perhydrotriazines by moderate heating and into bis(4-aminoaryl) methane derivatives or N-benzylarylamines, respectively when heated in acidic media with pH control. Reduction of N, O-acetals with sodium cyanoborohydride has revealed that the C-O bond is broken exclusively in acidic media.
Binding of acrylic and sulphonic polyanions by open-chain polyammonium cations
2000
Abstract The interactions between some acrylic and sulphonic polyanions and some protonated amines (diamines NH 2 -(CH 2 ) x -NH 2 , x =2,…,10; linear tri-, tetra-, penta- and hexa-amines) were studied potentiometrically in aqueous solution, at 25°C. For both types of polyanions AL 2 H i (L − , monomer of polyanion, A, amine) species are formed, with i =1,…, n ( n =number of amino groups in the amine). The stability of these species is strictly dependent on the polyammonium cation charge, and fairly independent of the type of amine (in diamine species maximum stability is observed for x =4, 5). Acrylic and sulphonic polyanion complexes are considerably stronger than analogous species formed…