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排序方式: 共有1307条查询结果,搜索用时 593 毫秒
31.
Ohno H Wakayama R Maeda S Iwasaki H Okumura M Iwata C Mikamiyama H Tanaka T 《The Journal of organic chemistry》2003,68(15):5909-5916
Alkyl radicals generated by treatment of thiocarbamates of conformationally favorable 3-alkyl-3-arylpropan-1-ols with tris(trimethylsilyl)silane and AIBN efficiently undergo intramolecular ipso substitution of the methoxy group, yielding the corresponding cyclized products. In contrast, either conformationally favorable or flexible 1-arylalkan-3- or 4-ones easily cyclize into five- or six-membered condensed rings by treatment with SmI(2) via ketyl radical intermediates. The addition of HMPA as cosolvent dramatically changes the cyclization mode of the SmI(2)-induced reaction, and the para-cyclization products are exclusively formed. This "HMPA effect" can be rationalized by the strong chelating ability of HMPA with the samarium atom. 相似文献
32.
Imai M Tanaka M Tanaka K Yamamoto Y Imai-Ogata N Shimowatari M Nagumo S Kawahara N Suemune H 《The Journal of organic chemistry》2004,69(4):1144-1150
Intermolecular hydroacylation between salicylaldehydes 1, 26-40 and 1,4-penta- or 1,5-hexadienes 4-13 by Rh-catalyst proceeded under mild reaction conditions to give a mixture of iso- and normal-hydroacylated products 14-25, 41-55, and 57-60. In the hydroacylation reaction, chelation of both salicylaldehyde and diene to the Rh-complex plays a crucial role. The ratio of iso- and normal-hydroacylated products could be regulated by the addition of salicylic acid or amines. The effects of various Rh-complexes, solvents, and additives were examined, and the plausible mechanisms of the catalytic cycle were proposed on the basis of the deuterium-labeling salicylaldehyde experiments. 相似文献
33.
Du YZ Hiratsuka Y Taira S Eguchi M Uyeda TQ Yumoto N Kodaka M 《Chemical communications (Cambridge, England)》2005,(16):2080-2082
A new nano-biomachine has been created from microtubules (MTs) and hetero-bifunctional polymer particles bearing pyruvate kinase, which is propelled on glass surfaces coated with kinesin by use of self-supplying ATP. 相似文献
34.
Masato Machida 《Catalysis Surveys from Asia》2002,5(2):91-102
(n)MnOx–(1?n)CeO2 binary oxides have been studied for the sorptive NO removal and subsequent reduction of NOx sorbed to N2 at low temperatures (≤150 °C). The solid solution with a fluorite-type structure was found to be effective for oxidative NO adsorption, which yielded nitrate (NO? 3) and/or nitrite (NO? 2) species on the surface depending on temperature, O2 concentration in the gas feed, and composition of the binary oxide (n). A surface reaction model was derived on the basis of XPS, TPD, and DRIFTS analyses. Redox of Mn accompanied by simultaneous oxygen equilibration between the surface and the gas phase promoted the oxidative NO adsorption. The reactivity of the adsorbed NOx toward H2 was examined for MnOx–CeO2 impregnated with Pd, which is known as a nonselective catalyst toward NO–H2 reaction in the presence of excess oxygen. The Pd/MnOx–CeO2 catalyst after saturated by the NO uptake could be regenerated by micropulse injections of H2 at 150 °C. Evidence was presented to show that the role of Pd is to generate reactive hydrogen atoms, which spillover onto the MnOx–CeO2 surface and reduce nitrite/nitrate adsorbing thereon. Because of the lower reducibility of nitrate and the competitive H2–O2 combustion, H2–NO reaction was suppressed to a certain extent in the presence of O2. Nevertheless, Pd/MnOx–CeO2 attained 65% NO-conversion in a steady stream of 0.08% NO, 2% H2, and 6% O2 in He at as low as 150 °C, compared to ca. 30% conversion for Pd/γ–Al2O3 at the same temperature. The combination of NOx-sorbing materials and H2-activation catalysts is expected to pave the way to development of novel NOx-sorbing catalysts for selective deNOx at very low temperatures. 相似文献
35.
3-Alkylthio-4-amino-1,6-dihydro-1,2,4-triazin-5(4H)-ones were synthesized by the reduction of 3-thio-4-amino-1,2,4-triazine-3,5(2.H,4H)-diones and successive S-alkylation. The regiospecific alkylation on the N-1 position or the exo amino group leads to a variety of 1,6-dihydro-1,2,4-triazin-5(4H)-one derivatives. An alternative synthesis of 3-thio-4-amino-1,6-dihydro-1,2,4-triazine-3,5(2H,4H)-diones was accomplished through the cyclization of 1-thiocarbohydrazidoacetamide derivatives. 相似文献
36.
4H-[1,3,4]Thiadiazolo[2,3-c][1,2,4]triazin-4-ones were prepared by cyclization of 3-thio-4-amino-1,2,4-tri-azine-3,5(2H,4H)-diones with a variety of acids in the presence of concentrated sulfuric acid. The synthesis appears to be general. 相似文献
37.
Nishibayashi Y Milton MD Inada Y Yoshikawa M Wakiji I Hidai M Uemura S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(5):1433-1451
The scope and limitations of the ruthenium-catalyzed propargylic substitution reaction of propargylic alcohols with heteroatom-centered nucleophiles are presented. Oxygen-, nitrogen-, and phosphorus-centered nucleophiles such as alcohols, amines, amides, and phosphine oxide are available for this catalytic reaction. Only the thiolate-bridged diruthenium complexes can work as catalysts for this reaction. Results of some stoichiometric and catalytic reactions indicate that the catalytic propargylic substitution reaction proceeds via an allenylidene complex formed in situ, whereby the attack of nucleophiles to the allenylidene C(gamma) atom is a key step. Investigation of the relative rate constants for the reaction of propargylic alcohols with several para-substituted anilines reveals that the attack of anilines on the allenylidene C(gamma) atom is not involved in the rate-determining step and rather the acidity of conjugated anilines of an alkynyl complex, which is formed after the attack of aniline on the C(gamma) atom, is considered to be the most important factor to determine the rate of this catalytic reaction. The key point to promote this catalytic reaction by using the thiolate-bridged diruthenium complexes is considered to be the ease of the ligand exchange step between a vinylidene ligand on the diruthenium complexes and another propargylic alcohol in the catalytic cycle. The reason why only the thiolate-bridged diruthenium complexes promote the ligand exchange step more easily with respect to other monoruthenium complexes in this catalytic reaction should be that one Ru moiety, which is not involved in the allenylidene formation, works as an electron pool or a mobile ligand to another Ru site. The catalytic procedure presented here provides a versatile, direct, and one-step method for propargylic substitution of propargylic alcohols in contrast to the so far well-known stoichiometric and stepwise Nicholas reaction. 相似文献
38.
Oka H Suzuki M Harada K Iwaya M Fujii K Goto T Ito Y Matsumoto H Ito Y 《Journal of chromatography. A》2002,946(1-2):157-162
pH-Zone-refining counter-current chromatography was successfully applied to the separation of the main components of Food Color Red No. 106 (R-106, acid red, Color Index No. 45100). A 300-mg quantity of sample was separated using the following two-phase solvent system: n-butanol-water, 40 mM sulfuric acid in organic stationary phase and 30 mM ammonia in aqueous mobile phase. The obtained fractions were analyzed by high-performance liquid chromatography and fast atom bombardment mass spectrometry. The separation yielded 261.9 mg of main component of acid red with purity of 99.9%. 相似文献
39.
Kodera M Shimakoshi H Nishimura M Okawa H Iijima S Kano K 《Inorganic chemistry》1996,35(17):4967-4973
A mononucleating tripyridine ligand, 2-(bis(2-pyridyl)methyl)-6-methylpyridine (L(1)), and a dinucleating hexapyridine ligand, 1,2-bis[2-(bis(2-pyridyl)methyl)-6-pyridyl]ethane (L(2)), have been prepared. The reaction of a carbanion of 2,6-lutidine with 2-bromopyridine affords L(1) which is converted to L(2) quantitatively by treating with tert-butyllithium and 1,2-dibromoethane. (&mgr;-Oxo)bis(&mgr;-acetato)diiron(III) complexes [Fe(2)(O)(OAc)(2)(L(1))(2)](ClO(4))(2) (1) and [Fe(2)(O)(OAc)(2)L(2)](ClO(4))(2) (2) have been synthesized and characterized by means of infrared, UV/vis, mass, and M?ssbauer spectroscopies and by measuring magnetic susceptibility and cyclic voltammograms. All the spectral data are consistent with the (&mgr;-oxo)bis(&mgr;-acetato)diiron(III) core structure in both 1 and 2. A relatively strong molecular ion peak at m/z 865 corresponding to [{Fe(2)O(OAc)(2)L(2)}(ClO(4))](+) in a FAB mass spectrum of 2 suggests the stabilization of the (&mgr;-oxo)bis(&mgr;-acetato)diiron(III) core structure by L(2) in a solution state. The compound 2.DMF.2-PrOH.H(2)O, chemical formula C(44)Cl(2)Fe(2)H(51)N(7)O(16), crystallizes in the monoclinic space group C2/c with a = 22.034(6) ?, b = 12.595(5) ?, c = 20.651(7) ?, beta = 121.49(2) degrees, and Z = 4. The cation has 2-fold symmetry with the bridging oxygen atom on the 2-fold axis: Fe-(&mgr;-O) = 1.782(5) ?, Fe-O-Fe = 123.6(6) degrees, and Fe.Fe = 3.142(3) ?. The diiron(III) core structure of 2 seems to be stabilized by encapsulation of the ligand. Compound 2 is the first example of a discrete (&mgr;-oxo)bis(&mgr;-acetato)diiron(III) complex with a dinucleating ligand. 相似文献
40.
Yuichiro Haramoto Yoshiharu Kusakabe Masato Nanasawa Seiji Ujiie Stephan Mang Cladius Schwarzwalder 《Liquid crystals》2013,40(10):1393-1397
Side chain type ionic liquid crystalline polymers having a 4-(1,3-dioxan-2-yl)pyridinium structure in their mesogenic side chain were synthesized. These polymers exhibited the smectic A phase. The molecular weights of these ionic liquid crystalline polymers are very high, e.g. for compound 7 - 2 M w = 486 000. 相似文献