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51.
[IrCl(cod)]2 and [Cp*IrCl2]2 complexes catalyzed efficiently the Guerbet reaction of primary alcohols to beta-alkylated dimer alcohols in good yields. For instance, the reaction of 1-butanol in the presence of [Cp*IrCl2]2 (1 mol %), t-BuOK (40 mol %), and 1,7-octadiene (10 mol %) produced 2-ethyl-1-hexanol in 93% yield. Various primary alcohols undergo the Guerbet reaction under the influence of Ir complexes to give the corresponding dimer alcohols in good yields. This method provides an alternative direct route to beta-alkylated primary alcohols which are prepared by aldol condensation of aldehydes followed by hydrogenation. 相似文献
52.
alpha,beta,gamma,delta-Tetrakis(1-methylpyridinium-3-yl)porphine [T(3-MPy)P] and alpha,beta,gamma,delta-tetrakis(1-methylpyridinium-4-yl)porphine [T(4-MPy)P] have been found to react rapidly with cadmium to give coloured complexes in weakly alkaline media at room temperature. Simple and practical methods for the determination of cadmium at ng/ml levels by conventional and analogue derivative spectrophotometry have been proposed. The analogue method gives higher sensitivity. T(3-MPy)P gives higher sensitivity than T(4-MPy)P. The interference of various foreign cations and anions has also been examined and in many cases eliminated or reduced. Adsorption of the porphyrins and their cadmium complexes onto the glassware, which is usually observed under the conditions of reaction and causes significant errors in the determination, can be suppressed almost completely by addition of fairly large amounts of a salt such as sodium chloride. 相似文献
53.
The heat of immersion in water was measured at 25°C for three iron(III) oxides using a twin-type microcalorimeter. One of the samples was commercial α-Fe2O3 (sample C) and the other two (samples M and F) were prepared by calcining magnetite and iron(III) hydroxide in air at various temperatures, Tp, from 300 to 700°C. The samples were evacuated at outgassing temperature, To, between room temperature and 500°C at a pressure of 1 × 10?2?2.7 × 10?2N m?2 for 6 h. The heat of immersion, hi(J m?2), of samples C and M increased with an increase in To and showed the maximum hi at To =400°C, while sample F did not show the maximum up to To =500°C. The systematic correlation was not observed between hi and Tp of sample F. The heat of reproduction of the surface hydroxyl group on sample F was approximately estimated as 6.6 × 104 J mole?1 H2O. 相似文献
54.
An 8-endo selective Friedel-Crafts cyclization of vinyloxirane 8 with Co2(CO)6-complexed benzeneacetylene was found to give poly-functional eight-membered cyclic compound 9 in high yields. 相似文献
55.
The reaction of [(trimethylsilyl)imino]methyldiphenylphosphorane: Ph2MePNSiMe3 (I) with several acid anhydrides or alkyl isocyanates took place by the simple cleavage of silicon-nitrogen bond. In contrast the interaction of (I) with phenyl isocyanate, isothiocyanate or carbon disulphide led to addition-elimination reactions of the Wittig type. Detailed investigation in the case of phenyl isocyanate indicated the usual elimination of Ph2MePO is suppressed by the strong affinity of the trimethylsilyl group for anionic oxygen atom. 相似文献
56.
Hisao Yokota Masatsune Kondo Tsutomu Kagiya Kenichi Fukui 《Journal of polymer science. Part A, Polymer chemistry》1968,6(2):435-446
The kinetic behavior on the polymerization of formaldehyde with and without acidic catalyst, in liquid carbon dioxide, in the temperature range of 30 to 50°C. was investigated. In the polymerization without catalyst both the polymer yield and the degree of polymerization increased with reaction time and also with rising temperature. With acidic catalyst, such as acetic acid and dichloroacetic acid, both the polymer yield and the degree of polymerization increased more than that in the polymerization without catalyst. The overall rate of polymerization with and without acidic catalyst was expressed by the first-order rate equation with respect to monomer concentration. From the results it was concluded that the polymerizations belonged to a type of successive polymerization with rapid initiation and no termination. The rate constant and the activation energy of each elementary process of polymerization were estimated on the basis of the results. 相似文献
57.
Ai Ito Takamasa Amaki Ayako Ishii Kazuo Fukuda Ryu Yamasaki Iwao Okamoto 《Tetrahedron letters》2018,59(45):3994-3998
Aromatic amides bearing 2-azulenyl group on the amide nitrogen were synthesized and their structures were investigated. The π-electron density of the N-aryl group was found to influence the cis-trans conformational preferences of these compounds in solution. X-ray crystallography revealed that the plane of the 2-azulenyl ring has a strong tendency to lie coplanar with the amide plane when the azulene group is located on the same side as the amide oxygen atom. 相似文献
58.
59.
A measurement technique for depth profiling in a time-domain low-coherence interferometer has been proposed. The spatial variation of the optical path caused by a diffraction grating in the Littrow configuration produces a white-light interferogram. A one-dimensional charge-coupled device (1D-CCD) detector is used to measure the undersampled white-light interferogram. The position of the reflective boundary is calculated from the rate of phase change with spatial frequency, which is based on the sub-Nyquist sampling of the white-light interferogram in the frequency domain. 相似文献
60.
Mengfei Wang Dr. Kei Murata Prof. Kazuyuki Ishii 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(35):8994-9002
Mono- and di-nuclear tricarbonyl Re(I) tetraazaporphyrin complexes ( Re1TAP and Re2TAP ) are investigated and compared with Re(I) phthalocyanine complexes ( Re1Pc and Re2Pc ). Although Re2Pc is unstable in polar solvents, and easily undergoes demetallation reaction, the coordination of the TAP ligand significantly improves the tolerance toward polar solvents, affording more stability to Re2TAP . Additionally, the incorporation of [Re(CO)3]+ unit(s) and the TAP ligand results in remarkable positive shifts in both oxidation and reduction potentials. Consequently, the more positive oxidation potentials of the ReTAP complexes significantly increase the tolerance toward oxidation, while the reduction potential indicates that Re2TAP is suitable for a soluble electron acceptor. In contrast to Re1Pc and Re2Pc , Re1TAP and Re2TAP show unique broad Q bands, which can be attributed to the admixture of the π-π* and metal-to-ligand charge transfer characters, owing to the lowered π orbital energy in the TAP complexes. This study is useful for controlling electronic properties and realizing high stability in Pc analogues. 相似文献