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71.
Sigenari Suzuki Masabumi Yamaguchi Masao Onda Takesffi Sakaizumi Osamu Ohashi Ichiro Yamaguchi 《Journal of Molecular Structure》1981,73(1):41-47
Microwave spectra of thionyl chloride, SO35Cl2 and SO35Cl37Cl, in the frequency range 8–25 GHz have been analyzed. The rotational constants have been obtained from the low J transition frequencies. The rS coordinates of Cl atoms and the ro structure have been evaluated with some assumptions: r(S-O) = 1.435 ± 0.011± Å, r(S—Cl) = 2.072 0.005 Å, ∠ OSCl = 108.00 ± 0.06°, ∠ ClSCl = 97.15 ± 0.30°. Nuclear quadrupole coupling constants have been obtained for the SO35Cl2, species: xaa = ?25.02 ± 0.04 MHz, x(bb = ?0.25 ± 0.04 MHz, Xcc = 25.27 ± 0.08 MHz, and Xzz = ?96.75 MHz. The values obtained are compared with those of other workers. 相似文献
72.
Masao Kato 《Journal of polymer science. Part A, Polymer chemistry》1969,7(8):2405-2410
Solution polymerizations of o-, m- and p-hydroxystyrene with boron trifluoride etherate were investigated. The results of infrared and ultraviolet spectroscopic investigations of the polymers thus obtained indicate that p-hydroxystyrene polymer consisted mainly of the structure formed through the normal vinyl polymerization mechanism, whereas o- and m-hydroxystyrene polymers contained considerable portions of the structures due to the reaction of the vinyl group with the phenol nucleus. The rate of polymerization and the intrinsic viscosity of the polymer decreased in the order p-hydroxystyrene ? o-hydroxystyrene > m-hydroxystyrene. It was of interest that on the cationic polymerization only p-hydroxystyrene gave polymer of high molecular weight. Plausible polymerization mechanisms were considered. Solid-state polymerization of p-hydroxystyrene at solid carbon dioxide temperature with the use of boron trifluoride etherate was also investigated. Appreciable polymerization occurred only at fairly high catalyst concentrations. 相似文献
73.
Masao Nohara Masaki Hasegawa Hatsuhiko Harashina Yoichi Iitaka 《Journal of polymer science. Part A, Polymer chemistry》1988,26(10):2695-2704
Photoreactive polyamides having m- or 1 -type cyclobutane moiety were prepared via a topochemical photodimerization of 4-(3-oxo-3-phenyl-1-propenyl)benzoic derivatives,4 followed by polycondensation of cyclobutane dicarboxylate derivatives with diamines. From the spectral studies of resulted polyamides compared with the corresponding reference diamides, it was concluded that both types of polyamides were depolymerized photochemically to give the same type of amide derivative having chalcone moiety with a small amount of undefined side reaction. The cyclobutane ring of the m-dimer from 4-(3-oxo-3-phenyl-1-propenyl)benzoic acid in crystal is severely twisted presumably because of the enhanced steric repulsions between two pairs of adjacent substituents. The higher quantum yield of the m-dimer for the photocleavege, compared with that of the 1 -dimer, has been interpreted in terms of such steric repulsions by the strained structure of the m-dimer. 相似文献
74.
H Yamamoto T Arai K Masuda K Ikei H Hashimoto I Taguchi K Kinoshita 《Radioisotopes》1986,35(9):461-466
Multivariate statistical analyses using principal component analyses (PCA) and Mahalanobis' method were applied to the quality control of radioallergosorbent test (RAST). Mites and foods allergen were analyzed by PCA method, and foods allergen were analyzed by Mahalanobis' method. The vast differences in the distribution on titers among the mites and the foods were observed. To evaluate the results of a test and the quality of kits for test statistically, it should be better to use multivariate analyses such as PCA or Mahalanobis' method. 相似文献
75.
Summary The partial resolution of some drug enantiomers by counter-current extraction in an aqueous two-phase system using bovine serum albumin (BSA) or ovomucoid (OVM) as chiral discriminator is described. The phase system was prepared with dextran 40, polyethylene glycol and a protein. Ofloxacin (OFLX) enantiomer was well recognized by the BSA system, whereas the enantiomers of carvedilol (-blocker) and DG-5128 (a new oral hypoglycaemic drug) were hardly recognized by the OVM system. The distribution coefficients of (S)-, (R)- and rac-OFLX varied with pH. Good enantioselectivity for OFLX was obtained at relatively high pH ( pH 9). The crude optically enriched OFLX enantiomers were extracted from the aqueous fractions and finally purified by thin-layer chromatography. 相似文献
76.
Toshiharu Arai 《Tetrahedron letters》2004,45(30):5921-5924
A stereoselective total synthesis of (+)-cylindricine C has been achieved starting with (S)-N-Boc-2-pyrrolidinone. The key elements of this synthesis involve the sequence of reactions including BF3-mediated addition of the allyl Grignard reagent to the cyclic imine, spirocyclization via enamine formation, and intramolecular Michael addition to form the tricyclic core. 相似文献
77.
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
78.
The ionic conduction in the perovskite-type halides, CsPbCl3, CsPbCl3 and KMnCl3, was studied. Measurements were made of ac conductivity at temperatures from 150°C to the melting point, and of ionic transport number using the Tubandt, EMF and ion-blocking methods. The effects of impurity doping on the ionic conductivity of CsPbCl3 were also studied using the samples of composition, CsPb0.99M0.01Cl2.99 (M = Li, Na, K, Ag). It was concluded that these materials are halide-ion condcutors. The ionic conductivities of CsPbCl3 and CsPbBr3 are close to those of the well known halide-ion conductors, PbCl2 and PbBr2. The ionic transport numbers were found to be > 0.9 for CsPbCl3 and CsPbBr3, and about 0.99 for KMnCl3. The conduction was considered to be caused by the migration of halide-ion vacancies VX (X = Cl, Br). The activation energies for the migration of VX were 0.29 eV for CsPbCl3, 0.25 eV for CsPbBr3 and 0.39 eV for KMnCl3. The vacancy diffusion coefficients of these materials were found to be verylarge. However, the impurity doping did not increase the ionic conductivity markedly because of small dopant solubility. 相似文献
79.
Metallic Na formation in/on NaCl crystals with irradiation by electron or vacuum ultraviolet photons
Shigehiro Owaki Shigeko Koyama Masao Takahashi Masao Kamada Ryouichi Suzuki 《Radiation Physics and Chemistry》1997,49(6):609-615
Metallic Na was formed in/on NaCl single crystals by irradiating them with a variety of radiation sources, namely, 21 MeV electron pulses, an electron beam of 30 keV and photon fluxes in the VUV region. The physical states were analysed using several methods, optical absorption, lifetime measurement of positron annihilation, Auger electron spectroscopy and UV photoelectron spectroscopy. Metallic Na was obtained in different physical states; clusters were formed in bulk, thin layers (islands) and thick layers on the surface. 相似文献
80.
Ooi T Takahashi M Yamada M Tayama E Omoto K Maruoka K 《Journal of the American Chemical Society》2004,126(4):1150-1160
A series of (2,7-disubstituted-1,8-biphenylenedioxy)bis(dimethylaluminum) (2) has been readily prepared in situ by treatment of the requisite 2,7-disubstituted-1,8-biphenylenediol (1) with Me3Al (2 equiv) in CH2Cl2 at room temperature; this primarily relies on the successful establishment of a new synthetic procedure of 1 starting from inexpensive m-anisidine. Evaluation of 2 as a bidentate organoaluminum Lewis acid has been performed by the reduction of ketonic substrates using Bu3SnH as a hydride source in comparison to the conventional monodentate Lewis acid dimethylaluminum 2,6-xylenoxide (11), uncovering the significantly high activation ability of 2 toward carbonyl. Particularly, (2,7-dimethyl-1,8-biphenylenedioxy)bis(dimethylaluminum) (2a) exerted the highest reactivity, which has also been emphasized in the Mukaiyama aldol reaction. The structure of the bidentate Lewis acid 2 was unambiguously determined by single-crystal X-ray diffraction analysis of 2g possessing a bulky 3,5-di-tert-butylphenyl substituent, revealing the rigid dimeric assembly in the solid state. The double electrophilic activation of carbonyl substrate by 2a has been supported by low-temperature 13C NMR analysis as well as theoretical study using the Gaussian 98 program. Moreover, unique stereoselectivity has been observed in the 2a-promoted Mukaiyama Michael addition, and highly chemoselective functionalization of carbonyl compounds in the presence of their acetal counterparts has been realized using 2a. Finally, the effectiveness of 2a for the activation of ether functionality has been demonstrated in the Claisen rearrangement of allyl vinyl ethers. 相似文献