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1.
Alkylation of 1-dimethylamino-1-cyanomethanephosphonic acid diethyl ester (8), easily obtainable from diethyl phosphite and the 0,N-acetal 9, yields 1-alkyl derivatives 14. Elimination of HCN converts 14 into 1-phosphonoenamines 6. Carbonyl compounds react with 8 to give 1-cyanoenamines 15 which may be hydrolyzed to from the homologous carboxylic acid. Alternatively, deprotonation of 15 yields the homoenolate anions 17 which can be alkylated or hydroxyalkylated, permitting chain extension of carbonyl compounds through introduction of an α-carboxyl and a β-alkyl group. Acid catalyzed hydrolysis of 8 results in cleavage of the PC bond, leading to the corresponding α-dimethylamino alkanoic acids. A phosphonic acid 11 can be obtained from 8 by application of the silylester method. An unambigous assignment of E/Z-isomers of the cyanoenamines 15 has been derived from 13C-NMR spectroscopy. 相似文献
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Ammonium Chloro(thio)phosphate Betaines, a Class of Coordination-stabilized Chloro(thio)metaphosphates Ammonium chloro(thio)phosphate betaines behave like systems being in equilibrium with tert. amine and monomeric chloro(thio)metaphosphate. In solution at room temperature the amine component can be displaced by stronger donors. Mass spectra reveal the presence of ClPS2 as monomer and dimer, of ClPO2 by fragment ions of the dimer, trimer, and tetramer before reorganization takes place to form PXCl3 and P4X10 (X = O, S). Detection of ClPOS fails owing to fast equilibration into ClPO2 and ClPS2. 相似文献
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Burkhard Costisella Iris Keitel 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4):161-165
Abstract The 1-acetoxy-1-methylthiomethanephosphoryl compounds (4) are prepared from methylthiomethanephosphoryl derivatives (1) by electrolysis in 0.6 molar sodium acetate/acetic acid solution. The reaction of 1-acetoxy compounds (4) with halogen carriers gives the 1-halogen-1-methylthiomethane-phosphoryl derivatives 5, 7 and 8. The reaction of 4a under PTC-conditions results in cleavage of the P-C-bond. Die 1-Acetoxy-1-methylthiomethanphosphoryl-Verbindungen (4) wurden aus Methylthiomethanphos-phorylderivaten (1) durch Elektrolyse in 0.6 molarer Na-acetat/Essigsäure-Lösung dargestellt. Die Reaktion der 1-Acetoxyverbindungen mit Halogenüberträgern führt zu den 1-Halogen-1-methyl-thiomethanphosphorylderivaten 5, 7 und 8. Bei Reaktion von 4a unter PTC-Bedingungen beobachtet man eine Spaltung der P-C-Bindung. 相似文献
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Angelovski G Costisella B Kolarić B Engelhard M Eilbracht P 《The Journal of organic chemistry》2004,69(16):5290-5294
Azamacrocyclic fluorophores containing piperazine units were synthesized using sequential rhodium-catalyzed regioselective hydroformylation-reductive amination. A piperazine unit is introduced into the macrocycles to act simultaneously as electron donor and binding site. The macrocycles chelate divalent cations, either Zn2+ or Co2+, which considerably enhanced fluorescence. Complexation with Zn2+ was additionally confirmed by NMR. 相似文献
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Maximilian Zieringer Abel Garcia‐Bernabé Dr. Burkhard Costisella Prof. Dr. Heiko Glatz Dr. Willi Bannwarth Prof. Dr. Rainer Haag Prof. Dr. 《Chemphyschem》2010,11(12):2617-2622
This paper describes the behavior of various generations of polyglycerol dendrimers that contain a perfluorinated shell. The aggregation in organic solvents is based on supramolecular fluorous–fluorous interactions, which can be described by means of 19F NMR spectroscopy. In order to study the interaction and aggregation phenomena of dendrimers with perfluorinated shell and perfluoro‐tagged guest molecules we investigated [G3.5]‐dendrimer with a perfluorinated shell in the presence of perfluoro‐tagged disperse red. Noteworthy, the interaction intensities varied in an unexpected manner depending on the equivalents of perfluoro‐tagged guest molecules added to the dendrimers in solution which then formed supramolecular complexes based on fluorous–fluorous interactions. We found that these complexes aggregated around residual air in the solvent to form stable micron‐sized bubbles. Their sizes correlated with the interaction intensities measured for certain dendrimer–guest molecule ratios. Degassing of the solutions led to a quasi phase separation between organic and fluorous phase, whereby the dendrimers formed the fluorous phases. Regassing the sample with air afforded bubbles of the initial size again. 相似文献
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Antonia Neels Helen Stoeckli-Evans Burhkard Costisella Harald Jancke Kenneth D. Knudsen Philip Pattison 《Helvetica chimica acta》1999,82(1):35-43
The structure of [(dimethylamino)methylene]bis[phosphonic acid] dihydrate (C3H11NO6P2⋅2 H2O; 1 ) was solved ab initio from synchrotron powder X-ray diffraction data. The structure determination was based on direct methods combined with difference Fourier techniques, and the refinement was carried out using the Rietveld method. Using this high-quality diffraction pattern, it was possible to index a second phase which corresponds to the structure of the known [(dimethylamino)methylene]bis[phosphonic acid] monohydrate ( 2 ). [(Dimethylamino)methylene]bis[phosphonic acid] dihydrate ( 1 ) is monoclinic, space group P21/c, Z=4, with a=10.6644(1), b=9.1599(1), c=10.5213(1) Å, and β=98.353(1)°. The structure analysis indicates two non-equivalent P-atoms in the molecule of 1 which are also observed in the corresponding monohydrate 2 and unhydrated form 3 . All three compounds exhibit extended H-bonding networks which result in remarkably different 31P-NMR spectra. The [(dimethylamino)methylene]bis[phosphonic acids] 1 – 3 crystallize in the betaine-type structure which, therefore, contains two nonequivalent P-atoms. The −P(=O)(OH)2 and −P(=O)(OH)O− groups of 1 – 3 are involved in a number of strong H-bonds which can be characterized by the different 31P-NMR chemical shifts of the two P-atoms of 1 – 3 . 相似文献
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M. Mikołajczyk S. Grzejszczak A. Zatorski B. Mlotkowska H. Gross B. Costisella 《Tetrahedron》1978,34(20):3081-3088
A new and general synthesis of ketene S,S-thioacetals (1) and ketene O.S-thioacetals (6) which involves the Horner-Wittig reaction of carbonyl compounds with the metallated S,S- and O,S-thioacetals of formyl-phosphonates (4 and 5) is described. The Horner-Wittig reaction of 4 with aromatic aldehydes can be carried out under two-phase conditions. The generation of the carbanions from 4 and 5 as well as the course of their reaction with carbonyl compounds were studied by the low temperature 31P NMR spectroscopy. It was found that S,S-thioacetals of formylphospbonates (4) are very easily metallated in contrast to O,S-thioacetals of formyl-phosphonates (5) which form the lithium derivatives only on treatment with t-butyllitnium. No evidence was obtained from 31P NMR spectra supporting the formation of the lithium derivatives of 0,0-acetals of formyl-phosphonates (12). 相似文献
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