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71.
Carmen Almansa Elena Carceller M. Lluïsa García Alba Torrents Fèlix Serratosa 《合成通讯》2013,43(4):381-390
The title compound 1 has been synthesized from diol 3a, either directly or after protection of the two hydroxy groups as benzyl ethers, by an intramolecular Pauson-Khand bis-annulation, followed by catalytic hydrogenation and oxidation in overall yields ranging from 15% (free diol) to 35% (dibenzyl ethers). 相似文献
72.
A fatty epoxide (tetradecyl-oxirane) is reacted with diethyl acetamidomalonate in basic medium, with or without solvent under solid-liquid phase transfer catalysis with LiCl, or under microwave irradiation on supported reagents (KF/Al2O3/LiCl). The main product is a lactone which is formed after epoxide ring opening and subsequent cyclisation. We put here into evidence, for the first time, the conjugated advantages of “dry media” reactions, lithium salt effects and microwave irradiation. 相似文献
73.
Chiral α-bromonitriles were prepared with good chemical and optical yields starting from natural α-amino acids by dehydrating the corresponding α-bromoamides with thionyl chloride. The combined system α-bromonitriles/hydrogen peroxide was examined for the enantio- and diastereoselective oxidation of N-alkylimines in basic media at room temperature. The oxidation of N-tertiobutylarylimines leads to optically active oxaziridines with moderate enantiomeric excess. However, the oxidation of (S)-1-phenylethylarylimines affords the corresponding oxaziridines with good diasteromeric excess up to 97/3 as proved by gaseous-phase chromatography. 相似文献
74.
Reaction of 2-bromo-2-bromomethyl glutaric acid esters with tetraalkylammonium fluoride in HMPA, conveniently provides the corresponding dialkyl (E)-2-bromomethylene derivatives in good yields. 相似文献
75.
Farid Halet Ahmed Réda Yeddou Abdelmalek Chergui Salima Chergui Boubekeur Nadjemi Aïssa Ould-Dris 《Journal of Dispersion Science and Technology》2013,34(12):1736-1741
Cyanide is considered one of the most dangerous compounds for the environment. They are discharged by various industries: chemical and metallurgical processes (extraction of gold and silver) and food industries. Adsorption is among the most used processes for elimination of cyanides particularly for the low concentrations. In this work, the cyanide removal is carried out by adsorption onto activated carbons prepared from olive stones and coffee ground. So we can promote this by-product as an inexpensive adsorbent. The prepared activated carbons are characterized by scanning electron micrograph and by determination of the physicochemical properties and specific surface area. All the adsorption experiments were performed in batch mode on synthetic water cyanide (KCN) at pH 10.8–11.0 to avoid volatilization of very toxic HCN. To describe the adsorption kinetics, the kinetic models of pseudo-first-order, pseudo-second-order, and intra-particle diffusion were applied. The experimental equilibrium data for adsorption of free cyanide were analyzed by the Langmuir, Freundlich, and Temkin isotherm models. 相似文献
76.
Aïcha Mbarek Geneviève Chadeyron Daniel Avignant Damien Boyer Mohieddine Fourati Daniel Zambon 《Journal of Sol-Gel Science and Technology》2013,68(2):193-203
The sol–gel chemistry route has successfully been used to prepare samples of LnP5O14 (Ln = La, Gd) pentaphosphates from lanthanides chlorides and phosphorous pentoxide dissolved in isopropanol. Crystallized powders of single phase were obtained after calcination of gels at 350 °C. The structural characterizations of materials were investigated by means of X-ray diffraction as well as infrared and Raman spectroscopies, whereas their thermal behavior has been studied by differential thermal analyse and thermogravimetric analyses. Powders morphology was analyzed by means of scanning electron microscopy and laser granulometry. The photoluminescence properties of the Eu3+ ions in sol–gel derived LaP5O14 and GdP5O14 samples were investigated and compared with homologous samples synthesized by the conventional solid state reaction. 相似文献
77.
Thien Y Vu Prof. Anna Chrostowska Prof. Thi Kieu Xuan Huynh Prof. Saïd Khayar Prof. Alain Dargelos Katarzyna Justyna Dr. Beata Pasternak Prof. Stanisław Leśniak Prof. Curt Wentrup 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(44):14983-14988
Thermal reactions of N‐benzylidene‐ and N‐(2‐pyridylmethylidene)‐tert‐butylamines ( 5 and 13 ) under FVT conditions have been investigated. Unexpectedly, at 800 °C, compound 5 yields 1,2‐dimethylindole and 3‐methylisoquinoline. In the reaction of 13 at 800 °C, 3‐methylimidazo[1,5‐a]pyridine was obtained as the major product. Mechanisms of these reactions have been proposed on the basis of DFT calculations. Furthermore, UV‐photoelectron spectroscopy combined with FVT has been applied for direct monitoring and characterization of the thermolysis products in situ. 相似文献
78.
Dr. Antoine Demont Dr. Carmelo Prestipino Dr. Olivier Hernandez Dr. Erik Elkaïm Serge Paofai Prof. Nikolaï Naumov Dr. Bruno Fontaine Prof. Régis Gautier Dr. Stéphane Cordier 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(38):12711-12719
The crystal structure of Cs2BaTa6Br15O3 has been elucidated by using synchrotron X‐ray powder diffraction and absorption experiments. It is built from edge‐bridged octahedral [(Ta6${{\rm Br}{{{\rm i}\hfill \atop 9\hfill}}}$ ${{\rm O}{{{\rm i}\hfill \atop 3\hfill}}}$ )${{\rm Br}{{{\rm a}\hfill \atop 6\hfill}}}$ ]4? cluster units with a singular poor metallic electron (ME) count equal to thirteen. This leads to a paramagnetic behaviour related to one unpaired electron. The arrangement of the Ta6 clusters is similar to that of Cs2LaTa6Br15O3 exhibiting 14‐MEs per [(Ta6${{\rm Br}{{{\rm i}\hfill \atop 9\hfill}}}$ ${{\rm O}{{{\rm i}\hfill \atop 3\hfill}}}$ )${{\rm Br}{{{\rm a}\hfill \atop 6\hfill}}}$ ]5? motif. The poorer electron‐count cluster presents longer metal–metal distances as foreseen according to the electronic structure of edge‐bridged hexanuclear cluster. Density functional theory (DFT) calculations on molecular models were used to rationalise the structural properties of 13‐ and 14‐ME clusters. Periodic DFT calculations demonstrate that the electronic structure of these solid‐state compounds is related to those of the discrete octahedral units. Oxygen–barium interactions seem to prevent the geometry of the octahedral cluster to strongly distort, allowing stabilisation of this unprecedented electron‐poor Ta6 cluster in the solid state. 相似文献
79.
Chengshuo Shen Dr. Emmanuel Anger Dr. Monika Srebro Dr. Nicolas Vanthuyne Dr. Loïc Toupet Prof. Christian Roussel Prof. Jochen Autschbach Prof. Régis Réau Dr. Jeanne Crassous 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(49):16722-16728
Homochiral and heterochiral cis‐bis‐cycloplatinated‐[6]helicene derivatives 1 b1, 2 , as representative examples of platina[6]helicenes that share a common platinum center, have been prepared. A diastereo‐ and enantioselective synthesis, which combines CH activation and dynamic isomerization from heterochiral structure 1 b2 into homochiral structure 1 b1 , is also described. Overall, this isomerization process results in the transfer of chiral information from one helicene moiety to the other one. The chiroptical properties of homochiral (P)‐ and (M)‐ 1 b1 were greatly modified upon oxidation into their corresponding (P)‐ and (M)‐diiodo‐PtIV complexes ( 5 ). The changes were also analyzed by performing theoretical calculations. C? H activation in the synthesis of organometallic helicenes is further demonstrated by the preparation of cis‐bis‐cycloplatinated‐[8]helicene 1 c . 相似文献
80.
Michael Biacchi Ricky Bhajun Nassur Saïd Alain Beck Yannis Nicolas François Emmanuelle Leize‐Wagner 《Electrophoresis》2014,35(20):2986-2995
mAbs are highly complex proteins that present a wide range of microheterogeneity that requires multiple analytical methods for full structure assessment and quality control. As a consequence, the characterization of mAbs on different levels is particularly product‐ and time‐consuming. CE‐MS couplings, especially to MALDI, appear really attractive methods for the characterization of biological samples. In this work, we report the last instrumental development and performance of the first totally automated off‐line CE‐UV/MALDI‐MS/MS. This interface is based on the removal of the original UV cell of the CE apparatus, modification of the spotting device geometry, and creation of an integrated delivery matrix system. The performance of the method was evaluated with separation of five intact proteins and a tryptic digest mixture of nine proteins. Intact protein application shows the acquisition of electropherograms with high resolution and high repeatability. In the peptide mapping approach, a total number of 154 unique identified peptides were characterized using MS/MS spectra corresponding to average sequence coverage of 64.1%. Comparison with NanoLC/MALDI‐MS/MS showed complementarity at the peptide level with an increase of 42% when using CE/MALDI‐MS coupling. Finally, this work represents the first analysis of intact mAb charge variants by CZE using an MS detection. Moreover, using a peptide mapping approach CE‐UV/MALDI‐MS/MS fragmentation allowed 100% sequence coverage of the light chain and 92% of the heavy chain, and the separation of four major glycosylated peptides and their structural characterization. 相似文献