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81.
Efficient monocyclic 1,2-diazepine formation via a tandem electrocyclization reaction of cyclobutenones with lithiodiazoacetate is demonstrated. The reaction proceeds through an oxy anion-accelerated 4π-ring opening of cyclobutene followed by an 8π-ring closure of the resultant oxy anion-substituted diazo-diene under mild conditions to furnish a 1,2-diazepine via formal diazomethylene insertion into the C-C bond of cyclobutenone. 相似文献
82.
A direct benzylic oxidation of alkylarenes via C-H bond abstraction was developed using alkali metal bromides and oxidants under mild conditions. This reaction proceeded with excellent selectivity by thermal oxidation or photooxidation to provide a broad range of carbonyl compounds containing electron-deficient aryl carbonyl compounds in high yields. 相似文献
83.
We found that La(2)Sb with a layered structure composed of alternate stacking of La square nets and LaSb layers exhibits bulk superconductivity with a critical temperature of 5.3 K. This suggests that the presence of the square net with strong La-La metal bonding is essential for the emergence of superconductivity. 相似文献
84.
Yuki Goto Masahiro Shiosaki Takeshi Hanamoto Masato Yoshida Hideo Sawada 《Colloid and polymer science》2013,291(5):1211-1217
Fluoro(silyl)acetylenes, which were prepared by reaction of 1,1-difluoroethylene with silyl chlorides, reacted with triethylamine to give dark-brown colored polyfluoro(silyl)acetylene powders in excellent to moderate isolated yields. In contrast, the corresponding nonfluorinated acetylene was unable to react with triethylamine at all to afford poly(silyl)acetylene under similar conditions. Polyfluoro(silyl)acetylenes thus obtained were nanometer size-controlled cubic fine particles with a good dispersibility and stability in a variety of solvents. These polyfluoro(silyl)acetylene nanoparticles exhibited clear absorption and emission spectra related to the conjugated units in polymer main chain. Furthermore, these polyfluoro(silyl)acetylene nanoparticles were applied to the surface modification of poly(methyl methacrylate) [PMMA] film to exhibit a higher oleophobicity imparted by fluorine on their surface, compared to that on the reverse side. Figure
New polyfluoro(silyl)acetylenes were prepared by reaction of the creesponding fluoro(silyl)acetylenes with triethylamine in excellent to moderate isolated yields. In contrast, the corresponding nonfluorinated silylacetylene was unable to give poly(silyl)acetylene under similar conditions. These polyfluoro(silyl)acetylenes thus obtained can form the nanometer size-controlled cubic fine particles (within 100 nm) in a variety of solvents. 相似文献
85.
Yoshihiro Abe Hideo Hosono Takayuki Kamae Kouichi Kawashima 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4):113-116
Abstract Protons in alkaline-earth phosphate glasses give much higher mobility than those in silicate glasses. This is caused by the difference in O-H bonding state. Protons in P-OH form a strong hydrogen bonding with oxygen anion, resulting in formation of weak O-H bond. The electrical conductivity of the glasses is proportional to the square of the proton concentration. The activation energy for the conduction is related to νOH, peak wavenumber of infrared absorption band (around~3000 cm?1), due to fundamental O-H stretching vibration. The mobility of protons increases with decreasing νOH, which depends on the species of ions included in the phosphate glasses. 相似文献
86.
Makoto Ojika Hideo Kigoshi Kiyotake Suenaga Yoshifumi Imamura Kohji Yoshikawa Takeshi Ishigaki Akira Sakakura Tsuyoshi Mutou Kiyoyuki Yamada 《Tetrahedron》2012,68(4):982-987
Five cytotoxic macrolides, aplyronines D–H (4–8), were isolated from the Japanese sea hare Aplysia kurodai. They are new congeners of the antitumor compound aplyronine A (1), which was previously isolated from the same organism. Their structures were determined by spectroscopic analysis (NMR and MS). The cytotoxicity of these new compounds was evaluated in comparison with that of aplyronines A–C (1–3), suggesting the importance of the 7-O-seryl ester group for mediating the potent cytotoxicity of aplyronines. 相似文献
87.
Aromatic ketones were efficiently prepared in good yields by the reactions of aryl bromides with n-BuLi, followed by the reactions with aromatic aldehydes or aliphatic aldehydes and the subsequent treatment with molecular iodine and K2CO3, in a one-pot method. The same treatment of arenes, instead of aromatic bromides, also provided the corresponding aromatic ketones in good yields. Using these methods, various diaryl ketones and alkyl aryl ketones bearing electron-rich aromatics and electron-deficient aromatics could be prepared efficiently by a simple, transition-metal-free, and therefore environmentally benign experimental procedure. 相似文献
88.
Atsutoshi Yamada Yuki Watanabe Kyoko Noda Sumitaka Itoh Koji Ishihara Masahiko Inamo Refat Moustafa Hassan Hideo D. Takagi 《Journal of solution chemistry》2014,43(9-10):1479-1486
The reduction reaction of the Cu(II)–pitn complex (pitn = 1,3-di(pyridine-2-carboxaldimino)propane) by decamethylferrocene [Fe(Cp*)2] was examined in acetonitrile. The observed pseudo-first-order rate constants exhibited saturation kinetics with increasing excess amount of [Fe(Cp*)2]. Detailed analyses revealed that the reaction is controlled by a structural change prior to the electron transfer step, rather than a conventional bimolecular electron transfer process preceded by ion pair (encounter complex) formation. The rate constant for the structural change was estimated to be 275 ± 13 s?1 at 298 K (?H* = 33.3 ± 1.0 kJ·mol?1, ?S* = 86 ± 5 J·mol?1·K?1), which is the fastest among gated reactions involving CuN4 complexes. It was confirmed by EPR measurement and Conflex calculations that the dihedral angle between the two N–N planes is significantly large (40°) in solution whereas it is merely 17.14° in the crystal. 相似文献
89.
Murahashi T Higuchi Y Katoh T Kurosawa H 《Journal of the American Chemical Society》2002,124(48):14288-14289
The linear sandwich tripalladium complexes [Pd3{Ar(CH=CH)4Ar}2[BArf]2 (Ar = Ph, p-t-Bu-C6H4, p-styryl-C6H4) undergo photoinduced isomerization involving face-inversion of the tetraene ligands. Irradiation of these complexes with visible light (>510 nm) resulted in rac (staggered sandwich) to meso (eclipsed sandwich) isomerization. The structures of rac and meso isomers are determined by X-ray crystallographic analyses. 相似文献
90.