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41.
Variants of the beta-aminophosphine L(1) [Ph(2)PCH(2)CH(Ph)NHPh] containing additional nitrogen donor functions have been prepared. These functions are branched off the C atom adjacent to the P atom, or the P atom itself. Ligand [Ph(2)PCH(o-C(6)H(4)NMe(2))CH(Ph)NHPh] has been obtained as a mixture of two diastereomers L(3A) and L(3B) by lithiation of L(2) [Ph(2)PCH(2)(o-C(6)H(4)NMe(2))] with n-BuLi followed by PhCH=NPh addition and hydrolysis. The diastereomers have been separated by fractional crystallization from ethanol. Ligand Et(2)NCH(2)P(Ph)CH(2)CH(Ph)NHPh has been obtained as a mixture of two diastereomers L(5A) and L(5B)(starting with P-Ph reductive cleavage of L(1) by lithium and subsequent hydrolysis to give PhP(H)CH(2)CH(Ph)NHPh (mixture of two diastereomers L(4A) and L(4B)). The latter reacts with diethylamine and formaldehyde to afford the L(5) diastereomeric mixture. Complexes RhCl(CO)(L) (L = L(3A), 1(A); L(3B), 1(B); L(5A/B), 2(A/B)) were obtained by reaction of [RhCl(CO)(2)](2) and the appropriate ligand or ligand mixture. Complexes 1(A), 1(B), and 2(A) have been isolated in pure form and characterized by classical techniques and by single-crystal X-ray diffraction. All structures exhibit a bidentate kappa-P,kappa-N(NHPh) mode similar to the complex containing L(1). While complexes 1(A) or 1(B) are stable in CDCl(3) solution, complex 2(A) slowly converts to its diastereomer 2(B). This unexpected epimerization appears to take place by inversion at the Rh-coordinated P center, an apparently unprecedented phenomenon. A mechanism based on a reversible P-C bond oxidative addition is proposed. The influence of the pendant nitrogen function of the diaminophosphines L(3A) and L(5A/B) on the rhodium catalytic activity in styrene hydroformylation has been examined and compared to that of the aminophosphines L(1) or L(2). The observed trends are related to the basicity of the dangling amine function and to its proximity to the metal center. 相似文献
42.
Kinetics of oil saponification by lead salts in ancient preparations of pharmaceutical lead plasters and painting lead mediums 总被引:1,自引:0,他引:1
M. Cotte E. Checroun J. Susini P. Dumas P. Tchoreloff M. Besnard Ph. Walter 《Talanta》2006,70(5):1136
Lead soaps can be found in archaeological cosmetics as well as in oil paintings, as product of interactions of lead salts with oil. In this context, a better understanding of the formation of lead soaps allows a follow-up of the historical evolution of preparation recipes and provides new insights into conservation conditions. First, ancient recipes of both pharmaceutical lead plasters and painting lead mediums, mixtures of oil and lead salts, were reconstructed. The ester saponification by lead salts is determined by the preparation parameters which were quantified by FT-IR spectrometry. In particular, ATR/FT-IR spectrometer was calibrated by the standard addition method to quantitatively follow the kinetics of this reaction. The influence of different parameters such as temperature, presence of water and choice of lead salts was assessed: the saponification is clearly accelerated by water and heating. This analysis provides chemical explanations to the historical evolution of cosmetic and painting preparation recipes. 相似文献
43.
Bérangère C Caussarieu N Morin P Morin-Allory L Lafosse M 《Journal of separation science》2004,27(12):964-970
An original system which uses Porous Graphitic Carbon as support and a mixture of organic solvents as mobile phase is proposed for the analysis of triterpenic acids by liquid chromatography. The separation of betulinic acid, ursolic acid, oleanolic acid, and 18alpha- and 18beta-glycyrrhetinic acids was carried out within a short time and monitored by evaporative light scattering detection as universal detection method. Molecular modelling studies show that the main contribution to the selectivity comes from the electrostatic interaction characterised by the dipole moment of the products. 相似文献
44.
Philippe Guerry Philippe Blanco Heinz Brodbeck Olivier Pasteris Reinhard Neier 《Helvetica chimica acta》1991,74(1):163-178
1-Methoxycarbonyl-Substituted 2,3-Dihydropyridin-4(1H)-one(= Methyl 1,2,3,4-Tetrahydro-4-oxopyridine-1-carboxylate) as Chromophore for Photochemical [2 + 2]-Cycloadditions With olefins having an electron-acceptor as well as with olefins having an electron-donor substituent, 1-methoxycarbonyl-substituted dihydropyridinone 12 undergoes [2 + 2] cycloaddition in good preparative yields. The photochemical cycloaddition is highly regioselective. For preparative purposes, the ring junction can be equilibrated to the thermodynamically more stable cis-junction. Only the ‘endo’/‘exo’ selectivity at the C-atom bearing the olefin substituent cannot be controlled. The photodimerization of 12 is the only side reaction. Using a slight excess of the olefin, the photodimerization can be suppressed. The protecting group at the N-atom of the dihydropyridinone can be varied in order to introduce an internal sensitizer, as shown with 1-acyl-substituted compound 29 , which underwent the cycloaddition process even with sunlight. 相似文献
45.
Upon hexanal-modification in the presence of NaCNBH(3), the oxidized B chain of insulin becomes mono- and further dialkylated on both the N-terminal and Lys(29) residues. A pseudo-MS(3) study was performed with a triple-quadrupole mass spectrometer on the different modified lysine-containing species to gain further insights into the characteristic fragmentation pattern. These fragmentations, in good agreement with true MS(3) measurements obtained using an ion trap mass spectrometer, highlighted characteristic monoalkylated lysine (immonium-NH(3)) and protonated modified caprolactam ions at m/z 168 and 213, respectively. In contrast, no fragment ion derived from a modified lysine residue (immonium or caprolactam) was observed when dialkylation occurs on Lys(29). However, a fragment ion corresponding to a protonated dihexylamine was observed at m/z 186. This loss, characteristic of dialkylated lysine fragmentation, was also observed upon dialkylation of N(alpha)-acetyllysine with either hexanal or pentanal. On the other hand, acetylation and malondialdehyde-modification of the N(alpha)-acetyllysine side chain led mainly to the corresponding modified (immonium-NH(3)) fragment ions at m/z 126 and 138, respectively. Finally, it was demonstrated that precursor ion scanning for both m/z 168 and 213 ions led to specific and sensitive identification of peptides containing hexanal-modified lysine residues within an unfractionated tryptic digest of hexanal-modified apomyoglobin. Thus, Lys(42), Lys(45), Lys(62), Lys(63), Lys(77), Lys(87), Lys(96), Lys(98), Lys(145) and Lys(147) were found to be modified upon reaction with hexanal. 相似文献
46.
Stéphanie Ricol Etienne Vernaz Philippe Barboux 《Journal of Sol-Gel Science and Technology》1997,8(1-3):229-233
Gels have been synthesized in the SiO2-Na2O-ZrO2 system and calcined at various temperatures up to 700°C. They have been studied by infrared absorption spectroscopy. The position of the asymmetric stretching frequency of the SiO4 unit is used as a tracer of the homogeneity. It is shown that sodium increases the solubility of zirconium in the silica matrix as already observed in fused glasses. 相似文献
47.
Andr Maquestiau Philippe Meyrant Robert Flammang 《Journal of mass spectrometry : JMS》1982,17(2):96-101
Molecular or fragment ions can be prepared by a large variety of reactions in the field free regions of a mass spectrometer; these reactions involve spontaneous dissociation as well as collision induced excitation of singly or doubly charged precursors. Some typical examples show the different means which can lead to a given ion and how they can be studied by collisional activation. It also appears that in most cases the use of a triple sector (E/B/E) mass spectrometer facilitates these experiments as interfering artefacts are suppressed. 相似文献
48.
[reaction: see text] An efficient method for the preparation of 3-aminofuran-2-carboxylate esters has been developed. This method is based on the reaction of an alpha-cyanoketone with ethyl glyoxylate under Mitsunobu conditions to produce a vinyl ether in good yield. Subsequent treatment of the vinyl ether with sodium hydride afforded the 3-aminofuran. It was also found that a one-pot procedure using the Mitsunobu reaction followed by cyclization afforded the 3-aminofuran in comparable yield. Currently, this method is limited to the synthesis of 5-alkyl-, 5-aryl-, and 4,5-fused bicyclic furans. 相似文献
49.
Roland Bonneau Philippe Fornier de Violet Jacques Joussot-Dubien 《Photochemistry and photobiology》1974,19(2):129-132
Abstract— The pH dependence of the apparent reactivity of thiazine dyes in their triplet states has been studied in aqueous solutions, using as electron donor HY-3 , the trianionic species of ethylene diamine tetraacetic acid (EDTA), in the pH range 4–8. The pH dependence is found to be related to a change in the degree of protonation of the triplet excited dye. The apparent reactivity and lifetime of two differently protonated forms of thionine, azur B and methylene blue were determined by classical and dye-laser flash techniques, making it possible to evaluate the rate constant for electron abstraction of these molecules in their triplet states. It is found that: (a) protonation on the ring nitrogen increases the electron-abstraction rate constant of the triplet-state species about twenty-fold, and (b) methylation on the side amino groups decreases it. 相似文献
50.
Dr. Pradip Ghosh Sander de Vos Dr. Martin Lutz Dr. Frederic Gloaguen Prof. Dr. Philippe Schollhammer Dr. Marc-Etienne Moret Prof. Dr. Robertus J. M. Klein Gebbink 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(55):12560-12569
Homogeneous electrocatalytic proton reduction is reported using cobalt complex [ 1 ](BF4)2. This complex comprises two bis(1-methyl-4,5-diphenyl-1H-imidazol-2-yl)methane (HBMIM ) ligands that contain an acidic methylene moiety in their backbone. Upon reduction of [ 1 ](BF4)2 by either electrochemical or chemical means, one of its HBMIM ligands undergoes deprotonation under the formation of dihydrogen. Addition of a mild proton source (acetic acid) to deprotonated complex [ 2 ](BF4) regenerates protonated complex [ 1 ](BF4)2. In presence of acetic acid in acetonitrile solvent [ 1 ](BF4)2 shows electrocatalytic proton reduction with a kobs of ≈200 s−1 at an overpotential of 590 mV. Mechanistic investigations supported by DFT (BP86) suggest that dihydrogen formation takes place in an intramolecular fashion through the participation of a methylene C−H bond of the HBMIM ligand and a CoII−H bond through formal heterolytic splitting of the latter. These findings are of interest to the development of responsive ligands for molecular (base)metal (electro)catalysis. 相似文献