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41.
42.
Tamao K Asahara M Saeki T Toshimitsu A 《Angewandte Chemie (International ed. in English)》1999,38(22):3316-3318
Migration of NMe(2) from C(naphthyl) to Si and Si-Si and Si-C bond formation to give a 1,2-disilaacenaphthene skeleton occurred in the reaction of hypercoordinate dichlorosilanes bearing the 8-(dimethylamino)-1-naphthyl group with two equivalents of magnesium [e.g., Eq. (a)]. The intermediate was isolated as the 1-isopropoxy derivative after quenching the reaction mixture with isopropyl alcohol. 相似文献
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45.
Yoshihiko Ohishi Tomonori Kawabata Tetsuya Shishido Ken Takaki Qinghong Zhang Ye Wang Katsuomi Takehira 《Journal of molecular catalysis. A, Chemical》2005,230(1-2):49-58
M-MCM-41 catalysts (M: V, Cr, Fe, and Ga) prepared by direct hydrothermal synthesis (DHT) have been tested for dehydrogenation of ethylbenzene with CO2. The synthesized materials were characterized by X-ray diffraction (XRD), N2 adsorption (77 K), and diffuse reflectance UV–vis spectroscopic measurements. Cr-MCM-41 showed the highest activity among M-MCM-41 catalysts tested, resulting in the production of styrene with the conversion of 65% and the selectivity above 90%. The rate of styrene formation increased with increasing Cr loading up to 1.7 wt.%. It is suggested that Cr(VI)O4 in tetrahedral coordination is formed as an active monochromate species and reduced to Cr(III)O6 in octahedral coordination as a less active polychromate species during the reaction. Deactivated catalyst was regenerated by a treatment with gaseous oxygen or CO2, during which redistribution as well as reoxidation of polymeric Cr(III)O6 octahedra to monomeric Cr(VI)O4 tetrahedra was observed. The rate of CO formation increased together with that of styrene formation, while the rate of H2 formation decreased, with increasing partial pressure of CO2. It was confirmed that reverse water-gas shift reaction took place over Cr-MCM-41 by a separate experiment. The rate of CO formation during the dehydrogenation of ethylbenzene with CO2 over Cr-MCM-41 was well accounted for by assuming parallel occurrence of two reactions, i.e., direct oxidative dehydrogenation of ethylbenzene with CO2 and simple dehydrogenation of ethylbenzene thermodynamically assisted by reverse water-gas shift reaction. 相似文献
46.
Chemical conversion of various celluloses to glucose and its derivatives in supercritical water 总被引:16,自引:0,他引:16
The supercritical water biomass conversion system was designed and developed in our laboratory. The reaction vessel with cellulose sample was treated with this system at supercritical state of water for a designated period (3–105s) under the conditions of a tin bath temperature of 500°C and pressure of 35MPa. The recovered products of hydrolysates were then analyzed by high performance liquid chromatography. The obtained results indicated that a high amount of glucose and levoglucosan can be achieved from both celluloses I and II for 5–10s supercritical treatment, while that from starch for 3–5s treatment. Although this difference could be due to a difference in the molecular structure between cellulose and starch, a difference between celluloses I and II was not significant. Instead, an accessibility of the water towards cellulose molecules seemed to be significant for their chemical conversion. With the longer treatment, amounts of these compounds observed were decreased due to decomposition. Therefore, it may be concluded that, compared with acid hydrolysis or enzymatic saccharification, cellulose may be hydrolyzed to glucose and its derivatives more or less to the same degree as in corn starch under supercritical state. This finding suggests that the supercritical treatment can overcome the difficulties in hydrolyzing cellulose to glucose, found in the acid hydrolysis or enzymatic saccharification techniques. 相似文献
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48.
Aya Yoshimura Akihiro Nomoto Mari Uchida Hiroki Kusano Tomokazu Saeki Akiya Ogawa 《Research on Chemical Intermediates》2017,43(6):3433-3443
The functionalization of polysilanes is an important subject in materials science because functionalized polysilanes are expected to exhibit potentially innovative properties. This research aims at the addition of a water-shedding property to polysilanes by introducing perfluoroalkyl groups into their skeleton. The photoinduced iodoperfluoroalkylation of various vinylsilanes takes place successfully upon irradiation with a xenon lamp: vinylmonosilanes undergo iodoperfluoroalkylation with perfluoroalkyl iodides (RfI) regioselectively, and the corresponding perfluoroalkylated silanes are obtained in moderate to high yields. Detailed optimization of the photoinduced iodoperfluoroalkylation has been investigated to apply this method to the functionalization of polysilanes. Polysilanes having vinyl groups can be synthesized by the reductive coupling of dichlorovinylsilanes with samarium diiodide (SmI2) and samarium metal (Sm) upon irradiation with visible light. The synthesized vinylpolysilanes and RfI (about 1.0 mM CHCl3 solution) are coated on a glass plate sequentially, and then the following photoirradiation with light of a wavelength over 300 nm successfully adds an excellent water-shedding property to the glass plate. 相似文献
49.
Sonomi Arata Dr. Yuna Kim Prof. Norihisa Hoshino Dr. Keishiro Tahara Dr. Kiyonori Takahashi Dr. Tomofumi Kadoya Tomonori Inoue Prof. Takayoshi Nakamura Prof. Tomoyuki Akutagawa Prof. Jun-ichi Yamada Prof. Kazuya Kubo 《欧洲无机化学杂志》2023,26(12):e202300017
Unsymmetrical gold(III)-dithiolene complexes are potential candidates for molecular materials that exhibit thermal structural phase transitions. In this study, unsymmetrical ppy-gold(III) (ppy−=C-deprotonated-2-phenylpyridine(−)) complexes [AuC5] and [AuC6] coordinated by dithiolene ligands containing tetrathiafulvalene (TTF) skeletons with pentylthio (2-{bis(pentylthio)-1,3-dithiol-2-ylidene}-1,3-dithiol-4,5-dithiolate(2−)) and hexylthio groups (2-{bis(hexylthio)-1,3-dithiol-2-ylidene}-1,3-dithiol-4,5-dithiolate(2−)) were synthesized. Both complexes exhibited a large absorption band at approximately 508 nm, owing to intramolecular ligand-to-ligand charge transfer. One-dimensional columnar structures with head-to-tail molecular arrangements around the metal ions were constructed in the crystals. The flexible alkylthio groups were intercalated into crystalline spaces between dithiolene ligands in the columns. [AuC5] exhibits a simple phase transition at 198 °C between crystalline and isotropic phases irreversibly. The crystalline phase of [AuC6] observed at 25 °C melted at 148 °C. Another crystalline phase grew above 148 °C with a very slow crystallization rate from the liquid phase and was completely transformed into an isotropic phase at 200 °C. 相似文献
50.
Let
be a smooth map of a closed n-dimensional manifold (n2) into the plane and let
be an orthogonal projection. We say that f has the standard lifting property, if every embedding
with
is standard in a certain sense. In this paper we give some sufficient conditions for a generic smooth map f to have the standard lifting property when M is a closed surface or an n-dimensional homotopy sphere. 相似文献