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31.
Reaction of the vicinal diols of steroids1, 5, 7, 10, 13, and16 with TPP/DEAD yields both regio-and stereospecifically the oxosteroids2, 6, 8, 11, 14, and15 by displacement of an axial hydrogen and extrusion ofTPPO besides the cholest-4-en-6-ols9 and12 and the cyclic carbonate3. 16, 17-androstandiol16 gives only the cyclic carbonate17. The different structures of the carbohydrates withcis-diol arrangement19 and21 lead exclusively to cyclic carbonates20 and22 in moderate yields. Treatment of1 with TPP/DEAD/HN3 affords 3-azido-2-hydroxycholestane4 in addition to the above mentioned2. 相似文献
32.
Addition of a small amount of polar solvent (i.e., modifier) to CO2 in packed column supercritical fluid chromatography (SFC) has shown major improvements in both polar analyte solubility and interaction of the polar analyte with the stationary phase. Recently, the addition of an ionic component (i.e., additive) to the primary modifier by one of us has been shown to extend even further the application of SFC to polar analytes. In this work, the effect of various ionic additives on the elution of ionic compounds, such as sodium 4-dodecylbenzene sulfonate and sodium 4-octylbenene sulfonate, has been studied. The additives were lithium acetate, ammonium acetate, tetramethylammonium acetate, tetrabutylammonium acetate, and ammonium chloride dissolved in methanol. Three stationary phases with different degrees of deactivation were considered: conventional cyanopropyl, deltabond cyanopropyl, and bare silica. The effect of additive concentration and additive functionality on analyte retention was investigated. Sodium 4-dodecylbenzene sulfonate was successfully eluted using all the additives with good peak shape under isocratic/isobaric/isothermal conditions. Different additives, however, yielded different retention times and in some cases different peak shapes. 相似文献
33.
在硼氢化钾碱性溶液中对金属氢化物(MH)电极的表面进行化学还原处理,提高了MH电极的放电容量、活化性能和电催化活性.用其为负极组装的AA型MH-Ni电池进行了封口化成,电池放电容量达到1150mAh,5C下电池的放电容量达到0.2C下容量的80%以上,电池在1C100%DOD(放电深度)充放电条件下,循环寿命由原来的100次左右提高到200次以上 相似文献
34.
E. V. Tulyakova O. A. Fedorova Yu. V. Fedorov G. Jonusauskas A. V. Anisimov 《Russian Chemical Bulletin》2007,56(11):2166-2174
Using 1H NMR spectroscopy and steady-state and time-resolved electronic spectroscopy, the optical properties of mono-and bis(styryl)pyridinium
perchlorates and their complexes with Mg2+, Ba2+ cations were studied. The stability constants of the complexes were determined using spectrophotometric titration. The formation
of inclusion complexes for Mg2+ and sandwich type complexes for Ba2+ results in fluorescence enhancement and increases the lifetimes of the excited states of the initial bis-styryl ligands.
The variation of position of the styryl fragment in the pyridinium aromatic ring gives rise to photochromic crown ethers with
different optical and photophysical characteristics and is also an easy route to bis(crown-ethers) of symmetrical and unsymmetrical
structure.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2092–2100, November, 2007. 相似文献
35.
Study on flame-retardant mechanism of polycarbonate containing sulfonate-silsesquioxane-fluoro retardants by TGA and FTIR 总被引:1,自引:0,他引:1
Shumei Liu Yongsheng Zhou Zhijie Jiang Xianbo Huang 《Polymer Degradation and Stability》2006,91(8):1808-1814
The flame retardancy of bisphenol A polycarbonate (PC) containing potassium diphenylsulfone sulfonate (KSS), poly(aminopropyl/phenylsilsesquioxane) (PAPSQ) and poly(vinylidenefluoride) (PVDF) was measured by limited oxygen index (LOI) and examined according to UL94. A high LOI and UL94 V-0 rating for 1.6 mm thickness samples were obtained by a combined use of equivalent KSS, PAPSQ and PVDF at 0.1-0.3 wt% loading, respectively. The improvement in flame retardancy of PC compositions arose from the synergistic interaction of three additives. Thermogravimetric analysis (TGA) indicated that the combination decreased the activation energy (E) of PC degradation and elevated the thermal degradation rate of PC to ensure the formation of an insulating carbon layer. FTIR analysis showed that the LOI char of PC containing the three additives took on a highly cross-linking aromatic ester and ether structure. 相似文献
36.
The apparent molal volumes and compressibilities of NaCl, KCl, and CsCl in mixtures of 18-Crown-6 and water have been calculated from density and speed-of-sound measurements at 25°C. The partial molal volumes and compressibilities of the salts when all cations have formed complexes with 18-Crown-6 molecules have been evaluated. The sign and magnitude of the volume and compressibility changes of complex formation strongly suggest that the charge of the cation becomes very effectively screened by the crown ether. 相似文献
37.
The stability of hexacyanoferrate(II)-amine(methylamine, ethylenediamine, diethylenetriamine and tetraethylenepentamine) was determined potentiometrically. Species Fe(CN)6(A)H
j
(j–4)
(A=amine) are formed in all the systems investigated, with j=1...n+2 (n=number of aminogroups). Some other complexes Fe(CN)6(A)iHj (with i>1) were also found. The stability of these complexes is fairly high: the full protonated amine species, show for the reaction Fe(CN)6
4- + HnAn+ = Fe(CN)6(A)Hn
(n-4) an equilibrium constant given by logK=0.686+2.10n. Factors affecting the stability are discussed in comparison with similar systems, together with the importance of interferences. 相似文献
38.
Eric J.L. McInnes Grigore A. Timco Richard E.P. Winpenny 《Coordination chemistry reviews》2005,249(23):2577-2590
Studies of two distinct classes of chromium(III) cage complexes are discussed. The first are compact oxo- and carboxylate cages, made by heating precursors to high temperature under a flow of nitrogen. One of these cages, [Cr12O9(OH)3(O2CCMe3)15], has an S = 6 spin ground state which proves a very interesting subject for study by EPR and MCD spectroscopy. Use of other carboxylates leads to other octa- and dodeca-nuclear complexes. The second class of compounds are homo- and hetero-metallic wheels and chains bridged by fluoride and carboxylates. These include the first heterometallic anti-ferromagnetically coupled ring systems and are being widely studied in areas as diverse as magnetic cooling and quantum information processing. The mechanism by which these unusual cyclic and acyclic structures form is discussed. 相似文献
39.
Starting from the natural neo-clerodane diterpenoid teubotrin (1) several neo-clerodane derivatives (3-7,9-11) have been obtained. The naturally occurring diterpenoid teuscordinon (12) has also been synthesized from teubotrin (1), showing thereby how some of these transformations can be useful for the synthesis of other natural neo-clerodane diterpenes. The latter are of interest due to their activity as insect antifeedants and other important biological properties. 相似文献
40.
The heat of formation (H
f) of unsymmetrical ketone phenylhydrazones and their enehydrazine tautomers was calculated by the semi-empirical quantum-chemical AM1 method. It is concluded that from H
f values it is possible to judge the regioselectivity of indolization of unsymmetrical ketone phenylhydrazones.Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 220–221, January, 1993. 相似文献