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51.
Tadatomi Nishikubo Atsushi Kameyama Jun Yamashita Takahiro Fukumitsu Chika Maejima Masao Tomoi 《Journal of polymer science. Part A, Polymer chemistry》1995,33(7):1011-1017
The addition reaction of oxiranes ( 15a-d ) with carbon dioxide (CO2) was carried out using 1 mol % of soluble polymer-supported quaternary onium salts as catalysts under atmospheric pressure. The reaction of 15a-d with CO2 proceeded very smoothly to give the corresponding five-membered cyclic carbonates ( 16a-d ) in high yields at 90-100°C. The catalytic activity of the soluble polymer-supported quaternary onium salts was strongly affected by the following factors: kind of reaction solvent, degree of introduction of the pendant onium salt residues in the polymer chain, and type of alkyl group on the onium salts due to the balance between lipophilicity and steric hindrance of the onium salt residue. Furthermore, these soluble polymer-supported quaternary onium salts were found ordinarily to have higher catalytic activity than low molecular weight quaternary onium salts under the same reaction conditions. It was also found that the rate of reaction was proportional both to catalyst concentration and to oxirane concentration. © 1995 John Wiley & Sons, Inc. 相似文献
52.
Masao Matsuoka Tsuyoshi Matsuda June Tamaki Yoshifumi Yamamoto Chiaki Iwakura 《Research on Chemical Intermediates》2006,32(5):389-402
Laves-phase hydrogen storage alloy has a high potential for use as negative electrode material as alternative for the misch-metal-based
material. In order to improve the energy density and the rate capability of negative electrode, chemical and mechanical modification
of Lavesphase alloy with different stoichiometric ratios was carried out. Discharge capacity and high-rate dischargeabilty
was evaluated by electrochemical methods and the characterization of Laves-phase alloy was made by X-ray diffraction, SEM
observation and PCT measurement. The best result in discharge capacity could be obtained for stoichiometric Laves-phase alloy
with a composition of Zr0.9Ti0.1Ni1.1Co0.1Mn0.5V0.2Cr0.1 by boiling in 10 M KOH solution. On the other hand, the high-rate dischargeability was increased remarkably by introducing
mechanical grinding before alkali treatment. The cause for improved performance was discussed on the basis of thermodynamic
stability of metal hydride and changes in crystal structure and surface morphology influencing on diffusion coefficient and
diffusion path length of hydrogen. 相似文献
53.
Susumu Tajima Yukiyoshi Nagai Osamu Sekiguchi Masao Fujishige Nozomu Uchida 《Journal of the American Society for Mass Spectrometry》1995,6(3):202-206
The spontaneous unimolecular dissociation reaction of methyl lactate (1) ionized by electron impact was investigated by a combination of mass-analyzed ion kinetic energy spectrometry and deuterium labeling. The metastable ions 1+· decompose in a variety of ways: four fragment peaks are observed at m/z 89, 76, 61, and 45, which correspond to the losses of ?H3, CO, CH3?O, and ?OOCH3, respectively. Double hydrogen atom transfer occurs in the third reaction. The source-generated m/z 61 ions decompose into oxygen-protonated methanols at m/z 33 ([CH3OH 2 + ]) by the loss of CO with double hydrogen atom migration. Both hydroxyl and methyne hydrogen atoms in 1 +· are present in the resultant protonated methanols. 相似文献
54.
Hikaru HasegawaHisanori Senboku Yoshinori KajizukaKazuhiko Orito Masao Tokuda 《Tetrahedron》2003,59(6):827-832
Tandem cyclization of N-propargylaminyl radicals, generated by N-chlorination of (E)-alk-4-enylamines 2a-d and 2f followed by treatment with tributyltin radical, afforded 2-methylenepyrrolizidines 3a-d and 3f in a highly stereoselective manner. A similar radical cyclization of (Z)-N-propargyl-1-methyl-5-phenylpent-4-enylamine (2e) gave pyrrolizidine 3b having the same stereochemistry as that obtained from the E isomer 2b. 相似文献
55.
The cis,cis-[(bpy)(2)Ru(III)(OH(2))](2)O(4+) micro-oxo dimeric coordination complex is an efficient catalyst for water oxidation by strong oxidants that proceeds via intermediary formation of cis,cis-[(bpy)(2)Ru(V)(O)](2)O(4+) (hereafter, [5,5]). Repetitive mass spectrometric measurement of the isotopic distribution of O(2) formed in reactions catalyzed by (18)O-labeled catalyst established the existence of two reaction pathways characterized by products containing either one atom each from a ruthenyl O and solvent H(2)O or both O atoms from solvent molecules. The apparent activation parameters for micro-oxo ion-catalyzed water oxidation by Ce(4+) and for [5,5] decay were nearly identical, with DeltaH(++) = 7.6 (+/-1.2) kcal/mol, DeltaS() = -43 (+/-4) cal/deg mol (23 degrees C) and DeltaH(++) = 7.9 (+/-1.1) kcal/mol, DeltaS(++) = -44 (+/-4) cal/deg mol, respectively, in 0.5 M CF(3)SO(3)H. An apparent solvent deuterium kinetic isotope effect (KIE) of 1.7 was measured for O(2) evolution at 23 degrees C; the corresponding KIE for [5,5] decay was 1.6. The (32)O(2)/(34)O(2) isotope distribution was also insensitive to solvent deuteration. On the basis of these results and previously established chemical properties of this class of compounds, mechanisms are proposed that feature as critical reaction steps H(2)O addition to the complex to form covalent hydrates. For the first pathway, the elements of H(2)O are added as OH and H to the adjacent terminal ruthenyl O atoms, and for the second pathway, OH is added to a bipyridine ring and H is added to one of the ruthenyl O atoms. 相似文献
56.
Masao Kunioka Fumi Ninomiya Masahiro Funabashi 《Polymer Degradation and Stability》2007,92(7):1279-1288
The biodegradabilities of poly(?-caprolactone) (PCL) powders (av. size = 180.7 μm) in controlled compost at 58 °C have been studied using the microbial oxidative degradation analyzer (MODA) based on ISO 14855-2 entitled “Determination of the ultimate aerobic biodegradability of plastic materials under controlled composting conditions - Method by analysis of evolved carbon dioxide - Part 2: Gravimetric measurement of carbon dioxide evolved in a laboratory-scale test”. The biodegradability of the PCL powders was 101.4% in a 56-day test period by the ISO method. The biodegradabilities of PCL powders have been studied using percent modern carbon (pMC) measured by accelerated mass spectrometry (AMS). Trapped CO2 was analyzed by AMS to determine the pMC (sample) using 14C radiocarbon concentration. By using the theory that the pMC (sample) was the sum of pMC (compost) (104.88%) and pMC (PCL) (0%) as the respective ratios in the determined period, CO2 (respiration) was calculated only from one reaction vessel. The biodegradability of PCL powders was 79.9% in a 56-day test period by the AMS method. It was found that respiration activities in the sample vessel including PCL, compost and sea sand were the same as that in the blank vessel including compost and sea sand without PCL during the active biodegradation period (0-33 day) at 58 °C. It was confirmed that respiration activities in the sample vessel were slightly higher than that in the blank vessel after active biodegradation due to the propagation of microorganisms using energy and metabolites by PCL biodegradation during those periods. 相似文献
57.
Tsubaki H Tohyama S Koike K Saitoh H Ishitani O 《Dalton transactions (Cambridge, England : 2003)》2005,(2):385-395
Intramolecular pi-pi and CH-pi interactions between the bpy and PR3 ligands of fac-[Re(bpy)(CO)3(PR3)]+ affect their structure, and electrochemical and spectroscopic properties. Intramolecular CH-pi interaction was observed between the alkyl groups on the phosphine ligand (R =nBu, Et) and the bpy ligand, and intramolecular pi-pi and CH-pi interactions were both observed between the aryl group(s) on the phosphorus ligand (R =p-MeOPh, p-MePh, Ph, p-FPh, OPh) and the bpy ligand, while no such interactions were found in the trialkylphosphite complexes (R = OiPr, OEt, OMe). The intramolecular interactions distort the pyridine rings of the bpy ligand as long as 3.7 x 10(-2)A in crystals. Molecular orbital calculations of the bpy ligand suggest that this distortion decreases the energy gap between its pi and pi* orbitals. An absorption band attributed to the pi-pi*(bpy) transition of the distorted rhenium complexes, measured in a KBr pellet, was red-shifted by 1-5 nm compared to the complexes without the distorted bpy ligand. Even in solution, similar red shifts of the pi-pi*(bpy) absorption were observed. The redox potential E1/2(bpy/bpy*-) of the complexes with the trialkylphosphine and triarylphosphine ligand are shifted positively by 110-120 mV and 60-80 mV respectively, compared with those derived from the electron-attracting property of the phosphorus ligand. In contrast with these properties, three nu(CO) IR bands, which are sensitive to the electron density on the central rhenium because of pi-back bonding, were shifted to higher energy, and a Re(I/II)-based oxidation wave was observed at a more positive potential according to the electron-attracting property of the phosphorus ligand. 相似文献
58.
Polymeric pendant Ru(bpy)_3~(2+) complexes were prepared from homopolymer and copolymers of 4-methyl-4'-vinyl-2,2'-bipyridine (Vbpy). Vbpy was prepared from 4-methylpyridine. The comonomers were styrene (St), acrylic acid (AA), N-vinylpyrrolidone (Pyr), 4-vinylpyridine (Vpy), methyl methacrylate (MMA), 2-hydroxyethyl methacrylate (HEMA), acrylonitrile (AN) and N-ethyl-4-vinylpyridium bromide (EQ-Vpy). The fraction of the pendant Ru(bpy)_3~(2+) repeating unit in the polymeric complex was 0.022 to 0.052. Absorption maximum, molar extinction coefficient, emission maximum and relative emission intensity of the polymeric complexes were studied. 相似文献
59.
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
60.
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