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61.
The catalyst comprised [PdCl(η3-C3H5)]2 and a simple chiral hemilabile ferrocene ligand, 1′,2-bis(diphenylphosphinoethyl)ferrocenyl alcohol, provides synthetically acceptable results for an enantioselective Pd-catalyzed allylic alkylation of cyclohexanone derivatives bearing an electron-withdrawing group at the α-position to form the quaternary carbon with up to 90% enantioselectivity under mild reaction conditions. 相似文献
62.
Tsuyoshi Matsumoto Junji Furukawa Hirohisa Morimura 《Journal of polymer science. Part A, Polymer chemistry》1971,9(7):1971-1981
The π-allyl nickel halide-oxygen system was found to be active as catalyst for stereospecific polymerization of butadiene. The catalyst from π-allyl nickel chloride or π-allyl nickel bromide yields the polymer of 90% cis-1,4 content with high activity, whereas the catalyst from π-allyl nickel iodide affords a polymer of 70% or less cis-1,4 content. The catalyst systems can be fractionated into two parts on the basis of solubility in benzene. It is concluded that the catalyst activity originates essentially from the benzene-insoluble nickel complex which is composed of oxygen, halogen, σ-allyl group, and nickel. The structure of growing polymer terminal is discussed in relation to the mechanism of the stereospecific polymerization. 相似文献
63.
Junji Furukawa Eiichi Kobayashi Yoshihiro Arai Toshimitsu Suzuki Yoshinobu Takegami 《Journal of polymer science. Part A, Polymer chemistry》1976,14(10):2553-2563
An investigation by 220-MHz NMR spectroscopy was carried out on the alternating copolymers of acrylic monomer with 2-substituted 1,3-diolefin. The chain structures were determined. The acrylic monomers used were methyl methacrylate (MMA), acrylonitrile (AN), and methacrylonitrile (MAN); isoprene (IP) and chloroprene (CLP) were the 1,3-diolefins. In the MAN–IP alternating copolymer, the 1-position methylene protons of IP showed an AB quartet peak, confirming the α-1 linkage structure. Similarly, in the MMA–CLP and AN–CLP copolymers, the 1-position methylene protons of CLP showed and AB quartet and an ABX pattern, respectively, confirming the α-1 linkage structure in both these cases also. The α-1 linkage structure was also revealed by the decoupling technique in the MAN–CLP alternating copolymer. The AN–IP and MMA–IP alternating copolymers also possess a bond between the α-position of the acrylic monomer and the 1-position of IP. The monomeric units in the alternating copolymers of acrylic monomers with 2-substituted 1,3-diolefins were generally linked at the α-position of acrylic monomer and the 1-position of 1,3-diolefin. On the other hand, in the Diels-Alder adducts of acrylic monomer with 2-substituted 1,3-diolefin, the reaction takes place between the α-position of acrylic monomer and the 4-position of 1,3-diolefin. The regioselectivity of the alternating copolymers and the Diels-Alder adducts is quite compatible with the expectations from molecular orbital theory. 相似文献
64.
Junji Furukawa Shigenori Tsuruki Jitsuo Kiji 《Journal of polymer science. Part A, Polymer chemistry》1973,11(11):2999-3004
Alternating copolymerization of butadiene with several α-olefins and of isoprene with propylene were investigated by using a mixture of VO(Acac)2, Et3Al, and Et2AlCl as catalyst. The alternating copolymerization ability of the olefins decreases in the order, propylene > 1-butene > 4-methyl-1-pentene > 3-methyl-1-butene. The study on the sequence of the copolymer of isoprene with propylene by ozonolysis reveals that the polymer chain is reasonably expressed by the sequence \documentclass{article}\pagestyle{empty}\begin{document}$ \rlap{--} [{\rm CH}_{\rm 2} \hbox{--} {\rm CH} \hbox{=\hskip-1pt=} {\rm C(CH}_{\rm 3}) \hbox{--} {\rm CH}_{\rm 2} \hbox{--} {\rm CH(CH}_{\rm 3}) \hbox{--} {\rm CH}_{\rm 2} \rlap{--}]_n $\end{document}. NMR and infrared spectra indicate that the chain is terminated with propylene unit, forming a structure of ?C(CH3)? CH2? C(CH3)?CH2 involving a vinylene group. 相似文献
65.
A simple detection method to observe the uniplanar orientation behavior of native cellulose microfibrils to the cell wall surface by using Fourier transform infrared (FTIR) spectroscopy in the transmission mode is reported. Four bands at 1372, 1355, 1337, and 1317 cm−1 (the latter two have been mentioned previously by Liang and Marchessault (1960, J. Polym. Sci. 43: 85–100)) were found to be sensitive to such orientation: the two middle bands at 1355 and 1337 cm−1 increase remarkably when the 0.60–61 nm lattice planes lie parallel to the cell wall surfaces. The reverse was true when the 0.53–54 nm lattice planes oriented preferentially. Polarization of the two bands at 1372 and 1355 cm−1 was parallel, while that of the other two bands at lower wavenumbers, i.e., at 1337 and 1317 cm−1, was perpendicular to the molecular axis of cellulose. These bands were assigned to OH-related motion, probably to in-plane OH bending, as reported by Maréchal and Chanzy (2000, J. Mol. Spectrosc. 523: 183–196). 相似文献
66.
Ishizaka T Miyanaga Y Mukai J Asaka K Nakai Y Tsuji E Uchida T 《Chemical & pharmaceutical bulletin》2004,52(8):943-948
The purpose of this study was to evaluate the bitterness of 18 different antibiotic and antiviral drug formulations, widely used to treat infectious diseases in children and infants, in human gustatory sensation tests and using an artificial taste sensor. Seven of the formulations were found to have a bitterness intensity exceeding 1.0 in gustatory sensation tests (evaluated against quinine as a standard) and were therefore assumed to have an unpleasant taste to children. The bitterness intensity scores of the medicines were examined using suspensions in water or an acidic sports drink. In the case of three macrolide antibiotic formulations containing erythromycin (ERYTHROCIN dry syrup), clarithromycin (CLARITH dry syrup for pediatric), and azithromycin (ZITHROMAC fine granules for pediatric use), the bitterness intensities of suspensions in acidic sports drinks were dramatically enhanced compared with the corresponding scores of suspensions in water. This enhancement could be predicted using the taste sensor. On the other hand, a reduction of bitterness intensity was observed for an acidic sports drink suspension of an amantadine product (SYMMETREL fine granules) compared with an aqueous suspension. This reduction in bitterness could also be predicted using the taste sensor output value. Thus, the taste sensor could predict whether or not suspension in an acidic sports drink would enhance or reduce the bitterness intensity of pediatric drug formulations, compared with suspensions in water. 相似文献
67.
Masao Kato Takao Shiraga Tatsumi Kimura Takashi Fukuda Hiro Matsuda Hachiro Nakanishi 《先进技术聚合物》2002,13(2):120-126
We synthesized some novel rigid NLO‐active maleimide copolymers bearing DR‐1 moieties ( PMPD , PHSD and PHND ). All copolymers exhibited high Tg's (190~197 °C), good solubilities for common solvents and excellent film‐forming properties. Dependence of film thickness on the d33 value for the poled copolymer films induced by corona poling was investigated and it was demonstrated that in less than thickness of 0.3 µm decrease of the thickness gives rise to remarkable increase in the d33 value. The poled copolymer films exhibited large d33 values (270 × 10?9 esu (film thickness 0.13 µm) for PMPD , 290 × 10?9 esu (0.12 µm) for PHSD and 350 × 10?9 esu (0.08 µm) for PHND ) as well as large r33 values (51.0 pmV?1 for PMPD and 60.4 pmV?1 for PHND ) which are significantly large compared to the value of LiNbO3 (31 pmV?1) as a typical EO material. The d33 values of the poled copolymers were kept constant even after standing 1000h at 80 °C, although a small decrease was observed at an initial stage. Further, the d33 values did not change up to ca. 123 °C upon heating at the rate of 10 °C/min in all cases. Copyright © 2002 John Wiley & Sons, Ltd. 相似文献
68.
Wang GC Zhou YH Morikawa Y Nakamura J Cai ZS Zhao XZ 《The journal of physical chemistry. B》2005,109(25):12431-12442
The decomposition of methanol on the Ni(111) surface has been studied with the pseudopotential method of density functional theory-generalized gradient approximation (DFT-GGA) and with the repeated slab models. The adsorption energies of possible species and the activation energy barriers of the possible elementary reactions involved are obtained in the present work. The major reaction path on Ni surfaces involves the O-H bond breaking in CH(3)OH and the further decomposition of the resulting methoxy species to CO and H via stepwise hydrogen abstractions from CH(3)O. The abstraction of hydrogen from methoxy itself is the rate-limiting step. We also confirm that the C-O and C-H bond-breaking paths, which lead to the formation of surface methyl and hydroxyl and hydroxymethyl and atom hydrogen, respectively, have higher energy barriers. Therefore, the final products are the adsorbed CO and H atom. 相似文献
69.
70.
Mori M Oyama Y Suzuki A Takahashi K Yamada M Miyano K Miyata H Takei H Hirata KS Kajita T Kihara K Nakahata M Nakamura K Ohara S Sato N Suzuki Y Totsuka Y Yaginuma Y Koshiba M Suda T Tajima T Fukuda Y Nagashima Y Takita M Kaneyuki K Tanimori T Beier EW Frank ED Frati W Kim SB Mann AK Newcomer FM Van Berg R Zhang W 《Physical review D: Particles and fields》1991,43(9):2843-2846