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排序方式: 共有317条查询结果,搜索用时 46 毫秒
21.
Makoto Uchimura Ryohei Ishige Masayuki Shigeta Yuki Arakawa Yosuke Niko Junji Watanabe Gen-Ichi Konishi 《Research on Chemical Intermediates》2013,39(1):403-414
We synthesized thermotropic liquid-crystalline polyesters in which 9,10-diphenylanthracene moieties are incorporated into the main chain type of polyester forming the chiral smectic C (Sm C*). The polymers were prepared by the isopropyltitanate-catalyzed reaction of biphenyldicarboxylic acid and the corresponding diols, with different ratios of diol of 9,10-diphenylanthracene moiety to the alkane diols (1, 5, and 10 mol %) under nitrogen atmosphere. The polymers exhibited thermotropic liquid crystals despite the presence of a bulky diphenylanthracene moiety in the main chain. The circular dichroism spectra revealed that a Sm C* phase was formed in the polymer with 1 mol % of anthracene moiety, although only an Sm A phase was formed in the other polymers. This is the first example of a Sm C* polyester containing a diphenylanthracene moiety in the main chain. Furthermore, we measured the optical properties of the polymers and found that they exhibited very high fluorescent efficiency. The fluorescence spectra of the thin film differed from that of a CH2Cl2 solution. 相似文献
22.
Dr. Ryu Yamasaki Dr. Masato Ohashi Kyotaro Maeda Takuya Kitamura Minami Nakagawa Korehito Kato Tetsushi Fujita Ryohei Kamura Kazuto Kinoshita Dr. Hyuma Masu Prof. Dr. Isao Azumaya Prof. Dr. Sensuke Ogoshi Prof. Dr. Shinichi Saito 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(10):3415-3425
A detailed study of the Ni‐catalyzed [4+3+2] cycloaddition reaction between ethyl cyclopropylideneacetate and dienynes has been conducted, resulting in the development of a new method for the synthesis of compounds containing nine‐membered rings. We studied the reactivity of various dienynes, together with their substituent and conformational effects. The mechanism of the reaction was probed by examining the stoichiometric reactions of the Ni complexes and dienynes. 相似文献
23.
Multiple Reaction Pathways Operating in the Mechanism of Vinylogous Mannich‐Type Reaction Activated by a Water Molecule
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A systematic search for reaction pathways for the vinylogous Mannich‐type reaction was performed by the artificial force induced reaction method. This reaction affords δ‐amino‐γ‐butenolide in one pot by mixing 2‐trimethylsiloxyfuran, imine, and water under solvent‐free conditions. Surprisingly, the search identified as many as five working pathways. Among them, two concertedly produce anti and syn isomers of the product. Another two give an intermediate, which is a regioisomer of the main product. This intermediate can undergo a retro‐Mannich reaction to give a pair of intermediates: an imine and 2‐furanol. The remaining pathway directly generates this intermediate pair. The imine and 2‐furanol easily react with each other to afford the product. Thus, all of these stepwise pathways finally converge to give the main product. The rate‐determining step of all five (two concerted and three stepwise) pathways have a common mechanism: concerted Si? O bond formation through the nucleophilic attack of a water molecule on the silicon atom followed by proton transfer from the water molecule to the imine. Therefore, these five pathways have comparable barriers and compete with each other. 相似文献
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Ryohei Yoshisaki Dr. Shinya Kimura Dr. Masashi Yokoya Prof. Dr. Masamichi Yamanaka 《化学:亚洲杂志》2021,16(14):1937-1941
Maltose is a ubiquitous disaccharide produced by the hydrolysis of starch. Amphiphilic ureas bearing hydrophilic maltose moiety were synthesized via the following three steps: I) construction of urea derivatives by the condensation of 4-nitrophenyl isocyanate and alkylamines, II) reduction of the nitro group by hydrogenation, and III) an aminoglycosylation reaction of the amino group and the unprotected maltose. These amphiphilic ureas functioned as low molecular weight hydrogelators, and the mixtures of the amphipathic ureas and water formed supramolecular hydrogels. The gelation ability largely depended on the chain length of the alkyl group of the amphiphilic urea; amphipathic urea having a decyl group had the highest gelation ability (minimum gelation concentration=0.4 mM). The physical properties of the supramolecular hydrogels were evaluated by measuring their thermal stability and dynamic viscoelasticity. These supramolecular hydrogels underwent gel-to-sol phase transition upon the addition of α-glucosidase as a result of the α-glucosidase-catalyzed hydrolysis of the maltose moiety of the amphipathic urea. 相似文献
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Dr. Masato Ohashi Ryohei Doi Prof. Dr. Sensuke Ogoshi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(7):2040-2048
This report describes the first Pd0‐catalyzed cross‐coupling of hexafluorobenzene (C6F6) with diarylzinc compounds to give a variety of pentafluorophenyl arenes. This reaction could be applied to other perfluoroarenes, such as octafluorotoluene, pentafluoropyridine, and perfluoronaphthalene, to give the corresponding polyfluorinated coupling products. The optimal ligand in this catalytic reaction was PCy3, and lithium iodide was indispensable as an additive for the coupling reaction. One of the roles of lithium iodide in this catalytic reaction was to promote the oxidative addition of one C?F bond of C6F6 to palladium. Stoichiometric reactions revealed that an expected oxidative‐addition product, trans‐[Pd(C6F5)I(PCy3)2], generated from the reaction of [Pd(PCy3)2] with C6F6 in the presence of lithium iodide, was not involved in the catalytic cycle. Instead, a transient three‐coordinate, monophosphine‐ligated species, [Pd(C6F5)I(PCy3)], emerged as a potential intermediate in the catalytic cycle. Therefore, we isolated a novel PdII complex, [Pd(C6F5)I(PCy3)(py)], in which pyridine (py) acted as a labile ligand to generate the transient species. In fact, in the presence of lithium iodide, this PdII complex was found to react smoothly with diphenylzinc to give the desired pentafluorophenyl benzene, whereas the same reaction conducted in the absence of lithium iodide resulted in a decreased yield of pentafluorophenyl benzene, which indicated that the other role of lithium iodide was to enhance the reactivity of the organozinc species during the transmetalation step. 相似文献
28.
Dr. Ryohei Yasukuni Prof. Nordin Félidj Dr. Leïla Boubekeur-Lecaque Stéphanie Lau-Truong Prof. Jean Aubard 《Chemphyschem》2020,21(22):2614-2619
Localized surface plasmon resonance (LSPR) excitation on the photochromic reaction of a diarylethene derivative (DE) was studied by surface enhanced Raman scattering (SERS). UV and visible light irradiations transform reversibly DE between open-form (OF) and closed-form (CF) isomers, respectively. A mixture of PMMA and DE (either OF or CF isomer) was spin-coated onto gold nanorods (GNRs) arrays, designed by electron beam lithography, with two localized surface plasmon resonances (LSPR) at distinct wavelengths, due to their anisotropy. The photochromic reaction rates from CF to OF isomers, under LSPR excitation, were monitored from SERS spectral changes under different polarizations, on the same GNR substrate to compare the effect of LSPR field strength. It appears that the photoisomerization rate was faster when LSPR was excited with the polarization parallel to the GNR long axis. The present results highlight a potential genuine mechanism, from near field LSPR excitation, involved in the photochromic enhancement of diarylethene photochromes. 相似文献
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