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991.
Umeda N Hirano K Satoh T Shibata N Sato H Miura M 《The Journal of organic chemistry》2011,76(1):13-24
The direct oxidative coupling of phenylazoles with internal alkynes proceeds efficiently in the presence of a rhodium catalyst and a copper oxidant accompanied by double or quadruple C-H bond cleavages. Thus, as a representative example, 4,5-diphenylpyrazolo[1,5-a]quinoline, 1-(1,2,3,4-tetraphenylnaphthalen-5-yl)pyrazole, and 1-(1,2,3,4,5,6,7,8-octaphenylanthracen-9-yl)pyrazole can be obtained selectively through the coupling of 1-phenylpyrazole and diphenylacetylene in 1:1, 1:2, and 1:4 manners, respectively. The reactions preferentially take place at the electron-deficient sites on the aromatic substrates. A comparison of reactivities of variously substituted and deuterated substrates sheds light on the mechanism of C-H bond cleavage steps. The reaction pathway is highly dependent on reaction conditions employed, especially on the nature of solvent. The influence of solvation of a key rhodacycle intermediate has been investigated computationally. In addition, some of the condensed aromatic products have been found to exhibit intense fluorescence in the solid state. 相似文献
992.
993.
Kazumasa Funabiki Akitsugu Shibata Keisuke Hatano Masaki Matsui 《Journal of fluorine chemistry》2009,130(4):444-448
Various chiral α-perfluoroalkyl-N-methylprolinols were prepared and their organocatalytic activities in an acyl transfer reaction of 4-nitrophenyl 2-methoxyacetate with methanol-d4 in chloroform-d were examined. As a result, α-trifluoromethyl-N-methylprolinol was a more effective acyl transfer catalyst than not only secondary α-perfluorobutyl- and n-butyl-N-methylprolinols but also tertiary α,α-bis(perfluorobutyl)-N-methylprolinol. 相似文献
994.
995.
The enantioselective [2 + 2 + 2] cycloaddition of 1,6-diynes with alpha-methylene lactones and cyclic ketones gave various chiral spirocyclic compounds. The reaction proceeded with high enantioselectivity when the rhodium-xylylBINAP complex was used as a chiral catalyst. Not only exo-methylene cyclic compounds but also exo-methylene acyclic compounds could be used as coupling partners for diynes. The present protocol provides access to a new chiral library possessing a quaternary carbon center, including a spirocyclic system. 相似文献
996.
Kato H Shibata I Yasaka Y Tsunoi S Yasuda M Baba A 《Chemical communications (Cambridge, England)》2006,(40):4189-4191
The reductive amination of aldehydes or ketones using Ph(2)SiH(2) or PhSiH(3) has been effectively promoted by the direct use of Bu(2)SnClH-pyridine N-oxide as a catalyst; this method has advantages in terms of its mild conditions and wide application to various carbonyls and amines, including aliphatic examples. 相似文献
997.
Lu L Kobayashi A Kikkawa Y Tawa K Ozaki Y 《The journal of physical chemistry. B》2006,110(46):23234-23241
How particles aggregate into an interesting dendritic structure has been the object of research for many years because of its importance in understanding physical processes involved and in designing novel materials. In this work, we for the first time describe an oriented attachment-based assembly mechanism for formation of different types of dendritic silver nanostructures at room temperature. It is found that the concentration of both AgNO(3) and p-aminoazobenzene (PA) molecules has a significant effect on the formation and growth of these novel nanostructures. Characterization by transmission electron microscopy (TEM) clearly shows that the dendritic silver nanostructures can be obtained through the preferential oriented growth along a crystallographically special direction. Interestingly, we observe that the oriented attachment at room temperature can also take place between relatively large single-crystalline silver particles with a diameter range from 20 to 60 nm, which may provide a new possibility for the design of novel metal nanostructures by using large metal nanoparticles as building blocks at room temperature. Moreover, a surface-enhanced Raman scattering (SERS) technique is used to investigate the role of PA molecules during the growth of the dendritic silver nanostructures. 相似文献
998.
Yasuo Saegusa Takeshi Iwasaki Shigeo Nakamura 《Journal of polymer science. Part A, Polymer chemistry》1994,32(2):249-256
Seven 1,3,4-thiadiazole-containing polyethers with reduced viscosities of 0.27–1.44 dL/g were synthesized by the high-temperature solution polycondensation of novel activated difluoride, 2,5-bis (4-fluorophenyl)-1,3,4-thiadiazole, with aromatic diols possessing a variety of ring structures. The expected chemical structures were confirmed by IR and 1H-NMR spectroscopy and elemental analysis. Of all the polymers, three polyethers were highly crystalline and soluble only in limited solvents such as concentrated sulfuric acid. The other polyethers were amorphous and dissolved easily in a variety of organic solvents including N-methyl-2-pyrrolidone (NMP), phenols, and chlorinated hydrocarbons. Colorless to slightly yellow-colored, transparent, and tough films could be cast from the NMP solutions of the amorphous polyethers. The mechanical properties of the films were excellent, and their tensile strength, elongation at break, and tensile moduli were in the ranges of 48–72 MPa, 5–7%, and 1.3–1.9 GPa, respectively. The amorphous polyethers had high glass transition temperatures of 204–299°C. All the polyethers were highly thermally and thermooxidatively stable and exhibited no weight loss up to 400°C, with 10% weight loss being recorded at 464–513°C in air. © 1994 John Wiley & Sons, Inc. 相似文献
999.
Nakahara H Lee S Krafft MP Shibata O 《Langmuir : the ACS journal of surfaces and colloids》2010,26(23):18256-18265
Effective additives to pulmonary surfactant (PS) preparations for therapy of respiratory distress syndrome (RDS) are being intensively sought. We report here the investigation of the effects of partially fluorinated amphiphiles (PFA) on the surface behavior of a model PS formulation. When small amounts of a partially fluorinated alcohol C(8)F(17)C(m)H(2m)OH (F8HmOH, m = 5 and 11) are added to the PS model preparation (a dipalmitoylphosphatidylcholine (DPPC)/Hel 13-5 peptide mixture) considered here, the effectiveness of the latter in in vitro pulmonary functions is enhanced. The mechanism for the improved efficacy depends on the hydrophobic chain length of the added PFA molecules. The shorter PFA, F8H5OH, when incorporated in the monolayer of the PS model preparation, promotes a disordered liquid-expanded (LE) phase upon lateral compression (fluidization). In contrast, the addition of the longer PFA, F8H11OH, reduces the disordered LE/ordered liquid-condensed (LC) phase transition pressure and promotes the growth of ordered domains (solidification). Furthermore, compression-expansion cycles suggest that F8H5OH, when incorporated in the PS model preparation, undergoes an irreversible elimination into the subphase, whereas F8H11OH enhances the squeeze-out phenomenon of the SP-B mimicking peptide, which is important in pulmonary functions and is related to the formation of a solid-like monolayer at the surface and of a surface reservoir just below the surface. F8H11OH particularly reinforces the effectiveness of DPPC in terms of minimum reachable surface tension, and of preservation of the integrated hysteresis area between compression and expansion isotherms, the two latter parameters being generally accepted indices for assessing PS efficacy. We suggest that PFA amphiphiles may be useful potential additives for synthetic PS preparations destined for treatment of RDS in premature infants and in adults. 相似文献
1000.
Atsushi Narumi Harumi Kaga Kosei Kawasaki Yasuo Taniguchi Toshifumi Satoh Toyoji Kakuchi 《Journal of polymer science. Part A, Polymer chemistry》2001,39(23):4061-4067
Glucosyl styrene ( 1a ), maltosyl styrene ( 1b ), and maltohexaosyl styrene ( 1c ) were prepared by the glycosylation of 4‐vinylbenzyl alcohol with the corresponding glycosyl trichloroacetimidates with boron trifluoride diethyl ether complex. The copolymerizations of 1a – 1c with styrene were carried out with 2,2′‐azobis(2‐methylpropionitrile) as an initiator in dry N,N‐dimethylformamide at 60 °C, and this was followed by deacetylation to produce amphiphilic polystyrenes with glucose ( 3a ), maltose ( 3b ), and maltohexaose ( 3c ) as hydrophilic segments. 3 showed various solubility characteristics that were dependent on the content of glucose residues, especially within a range of 20–50 wt %. The solubility characteristics of 3 , related to the copolymer composition, indicated that the hydrophilic property was remarkably improved with an increased number of glucose units, that is, in the order 3a < 3b ? 3c . The results described in this article provide useful information for the design of glycoconjugated architectures with desired amphiphilic properties. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 4061–4067, 2001 相似文献