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71.
微波固相法合成钠快离子导体Na5YSi4O12 总被引:6,自引:0,他引:6
应用微波方法合固相反应难于制备的Na5YSi4O12纯相,讨论了微波合成条件对产物的影响,与溶胶-凝胶法相比,微波法反应速率快,选择性强,合成的样品具有特异的聚集态,缺陷和微结构,从而导致离子导电活化能下降。 相似文献
72.
Toshio Fuchigami 《Journal of fluorine chemistry》2007,128(4):311-316
Recent studies on solvent effects on electrochemical partial fluorination are reviewed. At first, the historical background and some problems of electrochemical fluorination in organic solvents like acetonitrile (MeCN) are briefly mentioned. Ethereal solvents like dimethoxyethane (DME) and a mixture of DME and MeCN were found to improve both the yield and current efficiency for electrochemical fluorination since these solvent systems effectively suppress anode passivation and overoxidation of fluorinated products once formed during the electrolysis. It was also found that DME stabilizes radical cationic intermediates of 4-arylthio-1,3-dioxolan-2-ones and 3-phenylthiophthalide leading to α-fluorination while dichloromethane (CH2Cl2) destabilizes them leading to fluorodesulfurization. On the other hand, imidazolium ionic liquids and liquid fluoride salts like Et4NF·4HF and Et3N·5HF exhibited similar effects to CH2Cl2. Selective fluorination of hardly oxidizable phthalide was also achieved using a combination of two kinds of ionic liquids (imidazolium triflate and liquid fluoride salts). 相似文献
73.
Acylation reaction of anthracene with oxalyl chloride in the presence of [Emim]Cl-AlCl3 ionic liquid has been investigated. Pure 1,2-aceanthryenedione, which is used as intermediate of functional aromatic polymer material, was obtained by recrystalling the reaction mixture with aether and was determined by GC/MS, 1↑HNMR and FTIR analysis. The influences of various parameters, such as the contents of AlCl3 in [Emim]Cl-AlCl3, the amount of acylation agent, amount of [Emim]Cl-AlCl3, reaction temperature and reaction time were investigated. The optimum conditions were as follows: the molar fraction of AlCl3 in ionic liquid [x(AlCl3)] being 0.67, molar ratio of ionic liquid to anthracene being 2:1, molar ratio of oxalyl chloride to anthracene being 2:1, reaction temperature being 40℃ and reaction time being 6h. Under above conditions, the yield and selectivity of 1,2-aceanthrylenedione can reach 91.5% and 98.3% respectively. Further more, [Emim]Cl-AlCl3 ionic liquid, compared with metal halides such as AlCl3, was found to catalyze the reaction as a novel environmental friendly catalyst and solvent and can be reused. 相似文献
74.
Bradley Y.W. Man 《Tetrahedron letters》2005,46(44):7641-7645
The rate of the substitution reaction of (R)-3-chloro-3,7-dimethyloctane (1) with either methanol or benzyl alcohol in mixtures containing the ionic liquid [Bmim][N(CF3SO2)2] was monitored using 35Cl NMR spectroscopy. The enantiomeric excess of the product, (S)-3-methoxy-3,7-dimethyloctane (2a), was analyzed using chiral gas chromatography. This product showed a decreasing enantiomeric excess with increasing concentration of ionic liquid. The rate of reaction of substrate 1 in each case varied with the concentration of the ionic liquid. Polarity measurements of the solvent mixtures were undertaken by standard methods, which are compared both to each other and to the observed rates. Solvent reorganization and selective solvation are also each proposed as contributing to the difference in the observed rates of reaction. 相似文献
75.
A unique approach to non-covalent electron and energy transfer is described that is based on the formation of salt bridges between oppositely charged porphyrin units. A new class of electrostatically linked dimeric and pentameric porphyrins was synthesized by interaction of novel anionic boron containing porphyrins such as 5-(benzamidodecahydro-closo-dodecaborate)-10,15,20-triphenylporphyrin (N1) and meso-tetrakis-benzamidodecahydro-closo-dodecaborate)porphyrin (N2) and a variety of cationic meso-tetraarylporphyrin units. A bipyridine linked dimer (N1 · bpy · N1) was also prepared by employing N,N′-dimethyl-4,4′-bipyridinium (bpy) as a spacer between two mono-anionic species. A quinone-porphyrin dyad was also prepared for electron or energy transfer demonstration. All the synthesized assemblies were characterized by NMR, IR, UV-Vis, and mass spectroscopy. Significant spectral changes occurred in the absorption spectra of these non-covalent porphyrin assemblies compared to those of the reference monomers, indicating the presence of electronic interaction between the adjacent porphyrin units. Resonance light scattering was also used to study the formation of these assemblies in solution. 相似文献
76.
Jean-Claude Jacquesy 《Journal of fluorine chemistry》2006,127(11):1484-1487
This is a summary of a lecture presented at the 100th Anniversary, Moissan Symposium in Paris on Friday 10th November 2006.In HF/SbF5, Vinca alkaloids react selectively at the D’ring of the molecule. In the presence of CHCl3 (or CCl4), vinorelbine yields 20′,20′-difluoro-3′,4′-dihydrovinorelbine (vinflunine), presently in phase III experimentation for treatment of bladder cancer and non small cell lung cancer. 相似文献
77.
78.
WANG Yongtao GUO Xianwei LIN Zhiyuan YANG Yubo WU Lingqiao LIU Huan YU Haijun 《高等学校化学研究》2020,36(3):439-446
The sphene-type solid electrolyte with high ionic conductivity has been designed for solid-state lithium metal battery. However, the practical applications of solid electrolytes are still suffered by the low relative density and long sintering time of tens of hours with large energy consumption. Here, we introduced the spark plasma sintering technology for fabricating the sphene-type Li1.125Ta0.875Zr0.125SiO5 solid electrolyte. The dense electrolyte pellet with high relative density of ca. 97.4% and ionic conductivity of ca. 1.44×10-5 S/cm at 30℃ can be obtained by spark plasma sintering process within the extremely short time of only ca. 0.1 h. Also the solid electrolyte provides stable electrochemical window of ca. 6.0 V(vs. Li+/Li) and high electrochemical interface stability toward Li metal anode. With the enhanced interfacial contacts between electrodes and electrolyte pellet by the in-situ formed polymer electrolyte, the solid-state lithium metal battery with LiFePO4 cathode can deliver the initial discharge capacity of ca. 154 mA·h/g at 0.1 C and the reversible capacity of ca. 132 mA·h/g after 70 cycles with high Coulombic efficiency of 99.5% at 55℃. Therefore, this study demonstrates a rapid and energy efficient sintering strategy for fabricating the solid electrolyte with dense structure and high ionic conductivity that can be practically applied in solid-state lithium metal batteries with high energy densities and safeties. 相似文献
79.
The results of conductance measurements on pyridinium picrate, tetraphenylo-sonium picrate, potassium picrate, tetraphenylantimony picrate, tetrapropylam-monium, tetrafluoroborate, tetramethylammonium hexafluorophosphate ion association noncoulombic interaction in dimethyl sulfoxide (DMSO) at 25°C in the concentration range 1–15×10–4 M are reported. The data were analyzed by the Justice modification of the Fuoss–Hsia equation. Except for pyridinium picrate all salts studied were found to be associated.Application of the Justice Barthel–Bjerrum model of ion association permitted calculation of the noncoulombic portion of the potential of mean force, W
±. Ionic limiting conductances were calculated for six ions using known values of previously determined transport numbers. A table of most current limiting ionic conductances for a variety of ions in DMSO at 25°C has been established. 相似文献
80.
YiHU JueCHEN ZhangGaoLE ZhenChuCHEN QinGuoZHENG 《中国化学快报》2005,16(7):903-905
An efficient method is reported for the synthesis of phenacyl esters by reaction of carboxylic acids with a-bromoacetophenone promoted by potassium fluoride in ionic liquid [Bmim]PF6, the yield of the reaction is almost quantitative and the products are essentially pure. 相似文献