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1.
Cross‐Coupling of Organolithium with Ethers or Aryl Ammonium Salts by C−O or C−N Bond Cleavage 下载免费PDF全文
Ze‐Kun Yang Dong‐Yu Wang Hiroki Minami Hiroyuki Ogawa Takashi Ozaki Dr. Tatsuo Saito Dr. Kazunori Miyamoto Dr. Chao Wang Prof. Dr. Masanobu Uchiyama 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(44):15693-15699
Various aryl‐, alkenyl‐, and/or alkyllithium species reacted smoothly with aryl and/or benzyl ethers with cleavage of the inert C?O bond to afford cross‐coupled products, catalyzed by commercially available [Ni(cod)2] (cod=1,5‐cyclooctadiene) catalysts with N‐heterocyclic carbene (NHC) ligands. Furthermore, the coupling reaction between the aryllithium compounds and aryl ammonium salts proceeded under mild conditions with C?N bond cleavage in the presence of a [Pd(PPh3)2Cl2] catalyst. These methods enable selective sequential functionalizations of arenes having both C?N and C?O bonds in one pot. 相似文献
2.
meso‐Dibenzoporphycene has a Large Bathochromic Shift and a Porphycene Framework with an Unusual cis Tautomeric Form 下载免费PDF全文
Dr. Koji Oohora Ayumu Ogawa Tamaki Fukuda Dr. Akira Onoda Prof. Dr. Jun‐ya Hasegawa Prof. Dr. Takashi Hayashi 《Angewandte Chemie (International ed. in English)》2015,54(21):6227-6230
meso‐Monobenzoporphycene (mMBPc) and meso‐dibenzoporphycene (mDBPc), in which one or two benzene moieties are fused at ethylene‐bridged positions (meso‐positions) of porphycene, were prepared in an effort to further delocalize the π‐electrons within the porphycene molecule. mMBPc and mDBPc were fully characterized by mass spectrometry, 1H and 13C NMR spectroscopy, and X‐ray crystallography. The longest‐wavelength Q‐bands of mMBPc and mDBPc are red‐shifted by 92 nm and 418 nm, respectively, compared to that of the unsubstituted porphycene (Pc). Electrochemical measurements indicate that the HOMO is destabilized and the LUMO is stabilized by the fused benzene moieties at the meso positions. Furthermore, both XPS and theoretical studies support the presence of a cis tautomeric form in the ground state of mDBPc, despite the fact that essentially all known porphycene derivatives adopt the trans tautomeric form. 相似文献
3.
Gabriela Furlan Giordano Luis Carlos Silveira Vieira Angelo Luiz Gobbi Renato Sousa Lima Lauro Tatsuo Kubota 《Analytica chimica acta》2015
An integrated platform was developed for point-of-use determination of ethanol in sugar cane fermentation broths. Such analysis is important because ethanol reduces its fuel production efficiency by altering the alcoholic fermentation step when in excess. The custom-designed platform integrates gas diffusion separation with voltammetric detection in a single analysis module. The detector relied on a Ni(OH)2-modified electrode. It was stabilized by uniformly depositing cobalt and cadmium hydroxides as shown by XPS measurements. Such tests were in accordance with the hypothesis related to stabilization of the Ni(OH)2 structure by insertion of Co2+ and Cd2+ ions in this structure. The separation step, in turn, was based on a hydrophobic PTFE membrane, which separates the sample from receptor solution (electrolyte) where the electrodes were placed. Parameters of limit of detection and analytical sensitivity were estimated to be 0.2% v/v and 2.90 μA % (v/v)−1, respectively. Samples of fermentation broth were analyzed by both standard addition method and direct interpolation in saline medium based-analytical curve. In this case, the saline solution exhibited ionic strength similar to those of the samples intended to surpass the tonometry colligative effect of the samples over analyte concentration data by attributing the reduction in quantity of diffused ethanol vapor majorly to the electrolyte. The approach of analytical curve provided rapid, simple and accurate analysis, thus contributing for deployment of point-of-use technologies. All of the results were accurate with respect to those obtained by FTIR method at 95% confidence level. 相似文献
4.
5.
Keiki Kishikawa Yuki Furukawa Tomohiro Watanabe Michinari Kohri Tatsuo Taniguchi Shigeo Kohmoto 《Liquid crystals》2017,44(8):1332-1339
Blue phases (BPs) obtained by doping a commercially available liquid crystalline compound (4-butyl-N-(4-ethoxybenzylidene)aniline (EBBA)) with (2R,3R)-2,3-bis(4-octyloxyphenylbenzoyloxy)-N-(hydroxydecyl)succinimide (1) were highly stabilised by the addition of a small amount of alkane diols. Especially, addition of only 0.5 mol% of octane-1,8-diol increased the BP–Iso transition temperature by 10 K and widened the BP temperature range up to 35 K. A model stabilisation mechanism based on the construction of a hydrogen bond network in each disclination zone in BPs was proposed. 相似文献
6.
The transient heat transfer behavior in the case of heat removal from a cylindrical heat storage vessel packed with spherical particles was investigated experimentally for various factors (flow rate, diameter of spherical particles packed, temperature difference between flowing cold air and spherical particles accumulating heat, and physical properties of spherical particles). The experiments were covered in ranges of Reynolds number based on the mean diameter of spherical particles packed Red = 10.3–2200, porosity?=0.310 to 0.475, ratio of spherical particle diameter to cylinder diameterd/D = 0.0075–0.177 and ratio of length of the cylinder to cylinder diameterL/D=2.5–10. It was found that especially the flow rate and the dimension of spherical particles played an important role in estimating the transient local heat transfer characteristics near the wall of the cylindrical vessel in the present heat storage system. As flow rate and diameter of spherical particles were increased under a given diameter of the cylinder heat storage vessel, the mean heat transfer coefficient between the flow cold air and the hot spherical particles increased and the time period to finish removing heat from the vessel reduced. In addition, the useful experimental correlation equations of mean heat transfer coefficient between both phases and the time period to finish removing heat from the vessel were derived with the functional relationship of Nusselt numberNu d=f [modified Prandtl numberPr * (d/D), Red) and Fourier numberFo = f(d/D, L/D, Pr*, Red). 相似文献
7.
Toru Minami Ryoji Kouno Tatsuo Okauchi Mitsuharu Nakamura Junji Ichikawa 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):689-692
The α-phosphonovinyl anions, generated in situ from treatment of β-hetero-substituted vinyl-phosphonates 1a-c with LDA (or LTMP), were trapped with various electrophiles such as chlorotriorganosilanes, chlorotrimethylgermane, chlorotriorganotins, dimethyl disulfide, and halogen to afford the corresponding β-hetero-substituted α-functionalized vinylphosphonates 2–14 in good to excellent yields. The Friedel-Crafts reaction of α-(silyl) or α-(germyl)phosphonoketene dithioacetals 2, 9 or 4 with acid chlorides gave α-acylated phosphonoketene dithioacetals 15–19 in 53–91 % yields. The palladium-catalyzed cross-coupling reaction of β-ethoxy-α-(tributylstannyl)vinylphosphonate 13 with a variety of organic halides (R = acyl, allyl, aryl etc.) provided β-ethoxy-α-substituted vinylphosphonates 20–25 in good to moderate yields. The palladium-mediated cross-coupling reaction of α-(iodo)-vinyl-phosphonates 7, 14 with terminal acetylenes afforded α-alkynylated vinylphosphonates 26–29 in 69–83 % yields. 相似文献
8.
Mitsuji Yamashita Lakonda Nagaprasada Rao Valluru Krishna Reddy Motoki Maeda Tatsuo Oshikawa Masaki Takahashi 《Phosphorus, sulfur, and silicon and the related elements》2013,188(6-7):1661-1665
Novel pentofuranose analogs of phospha sugar derivatives were synthesized starting from 1-phenyl-2-phospholene 1-oxide ( 1 ). First, the allylic oxidation of 1-phenyl-2-phospholene 1-oxide ( 1 ) with CrO 3 in Ac 2 O-AcOH or 3-hydroxy-1-phenyl-2-phospholene ( 2 ) with MnO 2 afforded 1-phenyl-4-oxo-2-phospholene 1-oxide ( 3 ). The C-5 alkylation of 3 in the presence of NaH by using benzyl bromide or methyl iodide as electrophiles afforded the target title compounds. 相似文献
9.
Dr. Hiromi Oshita Takashi Suzuki Kyohei Kawashima Prof. Dr. Hitoshi Abe Prof. Dr. Fumito Tani Prof. Dr. Seiji Mori Prof. Dr. Tatsuo Yajima Prof. Dr. Yuichi Shimazaki 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(32):7649-7658
In order to gain new insights into the effect of the π–π stacking interaction of the indole ring with the CuII–phenoxyl radical as seen in the active form of galactose oxidase, we have prepared a CuII complex of a methoxy-substituted salen-type ligand, containing a pendent indole ring on the dinitrogen chelate backbone, and characterized its one-electron-oxidized forms. The X-ray crystal structures of the oxidized CuII complex exhibited the π–π stacking interaction of the indole ring mainly with one of the two phenolate moieties. The phenolate moiety in close contact with the indole moiety showed the characteristic phenoxyl radical structural features, indicating that the indole ring favors the π–π stacking interaction with the phenoxyl radical. The UV/Vis/NIR spectra of the oxidized CuII complex with the pendent indole ring was significantly different from those of the complex without the side-chain indole ring, and the absorption and CD spectra exhibited a solvent dependence, which is in line with the phenoxyl radical–indole stacking interaction in solution. The other physicochemical results and theoretical calculations strongly support that the indole ring, as an electron donor, stabilizes the phenoxyl radical by the π–π stacking interaction. 相似文献
10.
D. -J. Qian H. Nakahara K. Fukuda K. -Z. Yang 《Journal of Dispersion Science and Technology》2013,34(3):1031-139
Monolayers of europium complexes on water surface have been directly visualized in the gas-liquid expanded region at different temperatures using Brewster angle microscopy (BAM). The film texture with network patterns of the complex (C18)2 Eu(DBM)4 and hs evolution with time and temperature of the subphase were examined. The average linear cell dimension and the polygon areas have been analyzed as a function of time and the temperature. The mechanism of the domain growth is qualitatively discussed. 相似文献