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101.
Three new dimeric benzofuran derivatives, ligulacephalins A (1), B (2) and C (3), were isolated from the roots of Ligularia stenocephala MATSUM. ET KOIDZ. (Compositae) together with three known compounds, 5,6-dimethoxy-2-isopropenylbenzofuran (4), euparin (5) and (R)-(-)-hydroxytremetone (6). The structures of the new compounds were determined by spectroscopic evidence. The chiral HPLC analysis demonstrated that 1-3 occurred as a racemate. The absolute configurations of each enantiomer from 1-3 were elucidated on the basis of circular dichroism (CD) data. 相似文献
102.
Fujita M Kim WH Sakanishi Y Fujiwara K Hirayama S Okuyama T Ohki Y Tatsumi K Yoshioka Y 《Journal of the American Chemical Society》2004,126(24):7548-7558
The reaction of 4-substituted cyclohex-1-enyl(phenyl)iodonium tetrafluoroborate with tetrabutylammonium acetate gives both the ipso and cine acetate-substitution products in aprotic solvents. The isomeric 5-substituted iodonium salt also gives the same mixture of the isomeric acetate products. The reaction is best explained by an elimination-addition mechanism with 4-substituted cyclohexyne as a common intermediate. The cyclohexyne formation was confirmed by deuterium labeling and trapping to lead to [4 + 2] cycloadducts and a platinum-cyclohexyne complex. Cyclohexyne can also be generated in the presence of some other mild bases such as fluoride ion, alkoxides, and amines, though amines are less effective bases for the elimination. Kinetic deuterium isotope effects show that the anionic bases induce the E2 elimination (k(H)/k(D) > 2), while the amines allow formation of a cyclohexenyl cation in chloroform to lead to E1 as well as S(N)1 reactions (k(H)/k(D) approximately 1). Bases are much less effective in methanol, and methoxide was the only base to efficiently afford the cyclohexyne intermediate. Nucleophiles react with the cyclohexyne to give regioisomeric products in the ratio dependent on the ring substituent. The observed regioselectivity of nucleophilic addition to substituted cyclohexynes is rationalized from calculated LUMO populations, which are governed by the bond angles at the acetylenic carbons: The less deformed carbon has a higher LUMO population and is preferentially attacked by the nucleophile. 相似文献
103.
Masao Tomoi Yasunori Hosokawa Hiroshi Kakiuchi 《Journal of polymer science. Part A, Polymer chemistry》1984,22(6):1243-1250
The rate of reaction of alkyl halides with aqueous sodium acetate or cyanide catalyzed by phosphonium salts supported on insoluble polystyrene resins, and rates of ion-exchange of the chloride ion in the catalysts against the acetate ion, were studied as a function of catalyst particle size, the percentage of ring substitution, the morphology of polymer support, and distance between active site and polymer backbone. Rates of 1-bromooctane or benzyl chloride with macroporous, 7–25% ring-substituted catalysts increased with increasing ring substitution. Rates with macroporous catalysts increased as a heptamethylene spacer was introduced between the active site and the polymer backbone. Rates of ion-exchange with macroporous catalysts were facilitated with increasing ring substitution or by the introduction of the spacer chain. A relation between the catalytic activity of macroporous or microporous catalysts and ion-exchange rates under triphase conditions was discussed. 相似文献
104.
The mechanism of second H2O formation in fully reduced cytochrome c oxidase is examined by sequential additions of one electron and two protons to a [Fe(IV)O, Cu(II)] compound II, which is the final intermediate of first H2O formation. It is found that the addition of one electron induces the concerted proton–electron transfer from the CuB to FeO moieties with no energy barriers. The H2O molecule coordinating to the Cu atom is a key molecule for the proton transfer from the CuB moiety to the FeO and/or Fe–OH moieties. It is also found from the results in previous and the present works that one can realize the reduction process of dioxygen by fully reduced cytochrome c oxidase. 相似文献
105.
Seven new compounds were isolated from the roots of Ligularia dentata, including five bisabolane‐type sesquiterpenoids (bisabolane=1‐(1,5‐dimethylhexyl)‐4‐methylcyclohexane), namely (8β,10α)‐8‐(angeloyloxy)‐5,10‐epoxybisabola‐1,3,5,7(14)‐tetraene‐2,4,11‐triol ( 1 ), (8β,10α)‐8‐(angeloyloxy)‐5,10‐epoxythiazolo[5,4‐a]bisabola‐1,3,5,7(14)‐tetraene‐4,11‐diol ( 2 ), (1α,2α,3β,5α,6β)‐1,5,8‐tris(angeloyloxy)‐10,11‐epoxy‐2,3‐dihydroxybisabol‐7(14)‐en‐4‐one ( 3 ), (1α,2α,3β,5α,6β)‐2,5,8‐tris(angeloyloxy)‐10,11‐epoxy‐1,3‐dihydroxybisabol‐7(14)‐en‐4‐one ( 4 ), and (1α,2β,3β,5α,6β)‐1,8‐bis(angeloyloxy)‐2,3‐epoxy‐5,10‐dihydroxy‐11‐methoxybisabol‐7(14)‐en‐4‐one ( 5 ) (angeloyloxy=[(2Z)‐2‐methyl‐1‐oxobut‐2‐enyl]oxy), and two lactone derivatives, (2α,3β,5α)‐2‐(acetyloxy)‐9‐methoxy‐5‐(methoxycarbonyl)‐2,3‐dimethylheptano‐5‐lactone ( 6 ), and (2β,4β)‐2‐ethyl‐5‐hydroxy‐5‐(methoxycarbonyl)‐4,5‐dimethylpentano‐4‐lactone ( 7 ) (α/β denote relative configurations), together with (2E,4R,5S)‐2‐ethylidene‐5‐(methoxycarbonyl)‐4‐methylhexano‐5‐lactone ( 8 ), a known synthetic compound. Compound 2 is the first sesquiterpenoid derivative containing the uncommon benzothiazole moiety. The structures of 1 – 8 were established by spectroscopic methods, especially 2D‐NMR and MS analyses. 相似文献
106.
Application of integrated computer simulation approach to solid surfaces and interfaces 总被引:2,自引:0,他引:2
Abhijit Chatterjee Momoji Kubo Kazuo Teraishi Hiromitsu Takaba Yasunori Oumi Akira Miyamoto 《Catalysis Surveys from Japan》1998,2(2):133-153
The atomistic understanding of the structure, reactivity, and electronic properties of solid surfaces and interfaces are essential for the design of novel catalysts and electronics/photonics devices which have high-performance and unexplored properties. Computational chemistry is expected not only to rationalize the experimental results but also to predict new features. We have applied integrated computer simulation methods including quantum chemistry, periodic density functional theory, molecular dynamics, embedded atom method, and atomic force microscopy simulation to various topics related to solid surfaces and interfaces. In the present paper, we reviewed our recent activities on supported metal catalysts, metal clusters, atomic force microscopy simulation, high-temperature superconductors, tribology, Si semiconductor and V2O5 catalysts. Our activities also involve the generation of a lot of new computer simulation codes. We emphasize that the integrated computer simulation system provides not only methods for scientific studies but also a key technology for industrial innovations in research and development. 相似文献
107.
Chang CJ Nolan EM Jaworski J Okamoto K Hayashi Y Sheng M Lippard SJ 《Inorganic chemistry》2004,43(21):6774-6779
The synthesis of a difluorofluorescein monocarboxaldehyde platform and its use for preparing ZP8, a new member of the Zinpyr family of neuronal Zn(2+) sensors, are described. By combining an aniline photoinduced electron transfer (PET) switch and an electron-withdrawing fluorescein scaffold, ZP8 displays reduced background fluorescence and improved dynamic range compared to previous ZP probes. The bright sensor undergoes an 11-fold increase in fluorescence intensity upon Zn(2+) complexation (Phi = 0.03-0.35) with high selectivity over cellular concentrations of Ca(2+) and Mg(2+). In addition, sensors in the ZP family have been utilized for optical imaging in biological samples using two-photon microscopy (TPM). The cell-permeable ZP3 probe is capable of identifying natural pools of labile Zn(2+) within the mossy fiber synapses of live hippocampal slices using TPM, establishing the application of this technique for monitoring endogenous Zn(2+) stores. 相似文献
108.
Yoshioka Y Kawai H Sato T Yamaguchi K Saito I 《Journal of the American Chemical Society》2003,125(7):1968-1974
The G-selectivity for Cu(I)-mediated one-electron oxidation of 5'-TG(1)G(2)G(3)-3' and 5'-CG(1)G(2)G(3)-3' has been examined by ab initio molecular orbital calculations. It was confirmed that G(1) is selectively damaged by Cu(I) ion for both 5'-TG(1)G(2)G(3)-3' and 5'-CG(1)G(2)G(3)-3', being good agreement with experimental results. The Cu(I)-mediated G(1)-selectivity is primarily due to the stability of the Cu(I)-coordinated complex, [-XG(1)G(2)G(3)-,-Cu(I)(H(2)O)(3)](+). The Cu(I) ion coordinates selectively to N7 of G(2) of 5'-G(1)G(2)G(3)-3' rather than N7 of G(1). The G(2)-selective coordination induces the G(1)-selective trap of a hole that is created by one-electron oxidation and migrates to GGG triplet. Therefore, the radical cation of G(1) is selectively created in both 5'-TG(1)G(2)G(3)-3' and 5'-CG(1)G(2)G(3)-3', giving the G(1)-selective damage of 5'-G(1)G(2)G(3)-3'. 相似文献
109.
Steven A. Markgraf Yasunori Furukawa Masayoshi Sato 《Journal of Crystal Growth》1994,140(3-4):343-348
We report on the top-seeded solution growth of LiB3O5 from an excess B2O3 solution. Parameters investigated include the Li2O/B2O3 ratio, rotation rate, pulling rate, cooling rate, and seed direction. With careful control of the above parameters, we have grown clear crystals of 25 × 30 × 20 mm in size. Selected nonlinear optical properties of these crystals are reported. Observations concerning the occurrence of unstable growth (inclusions, hopper growth) are discussed, and methods to eliminate the unstable growth are suggested. 相似文献
110.
Shizuo Tokito Hiromitsu Tanaka Koji Noda Akane Okada Yasunori Taga 《Macromolecular Symposia》1998,125(1):181-188
Novel hole and electron transporting materials have been synthesized to improve the thermal stability of organic electroluminescent (EL) devices. Molecular structures of such hole and electron transporting materials were designed based on triphenylamine (TPA) and oxadiazole (OXD) moieties, respectively. It has been found that the resulting materials have high glass transition temperatures (Tg) over 100°C and the vacuum-deposited thin films are significantly thermally stable. For the two-layer EL devices using the novel hole transporting materials and the typical emitting material, tris(8-quinolinolato) aluminum, the thermal stability has been clearly seen to depend on the Tg of the hole transporting material; excellent thermal stability was achieved. For the three-layer EL device using the novel electron transporting material, good emission efficiency and good stability were achieved. The electron transporting materials have been also applied to the polymeric system with polyvinylcarbazole matrix. 相似文献