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71.
Metathesis of hex-1-ene in ionic liquids catalyzed by WCl6 was studied. The metathesis is preceded by isomerization of hex-1-ene to hex-2-ene, from which the main reaction product, viz., oct-4-ene, is derived. The WCl6-1-butyl-3-methylimidazolium tetrafluoroborate (BMIM·BF4) system efficiently catalyzes metathesis of linear olefin, the ionic liquid serving as the reaction medium by forming a stable homogeneous catalytic system with WCl6. The yields of the metathesis products increase with increasing reaction temperature. The addition of tin-containing promoters leads to a substantial increase in the reaction rate. In the WCl6-BMIM·BF4-SnBu4 system, the selectivity of the formation of oct-4-ene is significantly enhanced.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2094–2097, October, 2004. 相似文献
72.
Electrolysis of the system Ti(IV)–NH2OH–C6H6 in an 11 M H2SO4 solution shows that using an organic solvent (acetic acid, acetonitrile) during cathodically initiated amination of aromatic substrates permits the production of aromatic amines with the overall yield by hydroxylamine reaching 91%. Due to a chain mechanism of radical substitution, the benzene amination in electrolytes containing 5 M CH3COOH and 5.5 M CH3CN terminates largely upon consuming 70–75 and 50–55% of the charge required theoretically for a one-electron process. The maximum efficiency of electrochemical amination is observed at low hydroxylamine conversions and the overall current efficiency for mono- and disubstituted products of the benzene amination may exceed in these conditions 750%. 相似文献
73.
3-Diethylamino-5-phenyl-1,2,4-diselenazolium-tetrachloroniccolate(II) — Synthesis and Structure Bis-(N′, N′-diethyl-N-benzoylselenoureato)nickel(II) reacts with diphosgene in benzene to 3-diethylamino-5-phenyl-1,2,4-diselenazolium-tetrachloroniccolate(II). Its structure is confirmed by RKSA and ESCA. The compound consists of cations, which are planar fivemembered rings and of tetrahedral tetrachloroniccolate(II) anions. The complex is isomorphic with 3-diethylamino-5-phenyl-1,2,4-dithiazolium-tetrachloroniccolate(II). 相似文献
74.
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76.
H. Liu T. F. Yeh H. S. Lee T. A. Skotheim Y. Okamoto 《Journal of polymer science. Part A, Polymer chemistry》1992,30(5):879-885
2,6-Di-t-butylphenol and oligo(ethylene oxide) bound covalently to polyisocyanate were synthesized and characterized. The ionic conductivities of their Li, Na, and K phenolates were studied at various temperatures. The conductivities were in the range of 10?7?10?5 S/cm at 30°C. The conductivity of Na and K salts was approximately 102 greater than that of the Li salts. The t-butyl groups serve to dissociate K and Na ions from the phenoxide. The cations, therefore, are more mobile as a result increasing the conductivity. The temperature dependence of ionic conductivity suggests that the migration of ions is controlled by segmental motion of the polymer, shown by linear curves obtained in Vogel–Tammann–Fulchere plots. The polyisocyanate backbone is a rather stiff structure, however, a flexible oligo(ethylene oxide) side chain forms complexes with metal ion. Since the ion transport is associated with the local movement of polymer segments, the rigidity of the polymer backbone does not have much influence on the ion mobility. 相似文献
77.
Hans-Jürgen Buschmann Achim Zielesny Eckhard Schollmeyer 《Journal of inclusion phenomena and macrocyclic chemistry》2006,54(3-4):181-185
The complex formation of the macrocyclic ligand hemicucurbit[6]uril with various salts has been studied in aqueous solution. Due to the low solubility of this ligand the formation of complexes results in an increase of the amount of ligand present in solution. From these measurements the stability constants of the complexes formed are calculated. Hemicucurbit[6]uril only forms cation complexes with cobalt(II), nickel(II) and the uranylion. All other cations examined e.g. silver(I), lead(II) and copper(II) do not form detectable complexes in aqueous solution. For a better understanding of the complexation behaviour some quantum mechanical chemical calculations are performed with Gaussian.Dedicated to Prof. H. Möhwald on the occasion of his 60th birthday. 相似文献
78.
《Thermochimica Acta》2003,401(2):169-173
The heat capacity and the heat content of gallium nitride were measured by calvet calorimetry (320-570 K) and by drop calorimetry (670-1270 K), respectively. The temperature dependence of the heat capacity in the form Cpm=49.552+5.440×10−3T−2.190×106T−2+2.460×108T−3 was derived by the least squares method. Furthermore, thermodynamic functions calculated on the basis of our experimental results and literature data on the molar entropy and the heat of formation of GaN are given. 相似文献
79.
The localization of Terbium (Tb3+) cations binding to deionized bacteriorhodopsin (bR) has been studied by using spectroscopic methods. It was found that adding
Tb3+ cations to deionized bR affects the fluorescence lifetimes of tryptophan (Trp) in bR, the wavelength of fluorescence peak
shifts “blue” and the peak value of fluorescence decreases. It was also found that adding one Tb3+ cation to deionized bR can restore the purple state from its blue state obviously. The measurements of absorbance, fluorescence
and lifetime of fluorescence also show that when more than three Tb3+ cations are added, no further changes can be found. It is suggested that one Tb3+ specific binding site for the color-controlling is located on the exterior of the bR trimer structure to negatively charged
lipids near Trp-10 and Trp-12. Three Tb3+ cations binding per bR is needed for the regenerated bR. 相似文献
80.