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排序方式: 共有1975条查询结果,搜索用时 15 毫秒
31.
Masao Kato Hiroyoshi Kamogawa 《Journal of polymer science. Part A, Polymer chemistry》1966,4(7):1773-1782
The polymerization behavior of o-hydroxystyrene with free-radical and cationic initiators and without an initiator was examined. The structures thus obtained were estimated. Although polymerization behavior of o-hydroxystyrene was rather complicated, according to the results, it appeared that each polymerization more or less might simultaneously follow the two types of mechanisms: normal vinyl polymerization and polymerization through the addition to benzene nuclei. The proportion of addition to benzene nuclei was considered to be highest in the polymerization with BF3·(OEt)2 and lowest in that with azobisisobutyronitrile. Degrees of polymerization of these polymers were low in all cases (42–82). Some brief experiments on copolymerization of o-hydroxystyrene were carried out. 相似文献
32.
Masao Tomoi Satoru Ishigaki Yasushi Arita Hiroshi Kakiuchi 《Journal of polymer science. Part A, Polymer chemistry》1988,26(8):2251-2261
Polystyrene-bound 4-(1-pyrrolidino)pyridine moieties were prepared by the reaction of chloromethylated polystyrene resins with pyrrolidinopyridine derivatives containing hydroxyl groups. The supported amines were effective catalysts for acylations of tert-alcohols or enols, acylrearrangements, and diester synthesis from epoxides and anhydrides. Some of the low ring-substituted (8–15%) catalysts exhibited high activity comparable to that of 4-(N,N-dimethylamino)pyridine, though the activity was a little lower than that of 4-(1-pyrrolidino)pyridine. The recovered catalysts can be re-used, except for acyl rearrangements, without significant decrease in activity. 相似文献
33.
Ito S Nomura A Morita N Kabuto C Kobayashi H Maejima S Fujimori K Yasunami M 《The Journal of organic chemistry》2002,67(21):7295-7302
The Diels-Alder reaction of di-2-azulenylacetylene with tetraphenylcyclopentadienone afforded 7,8,9,10-tetraphenyldiazuleno[2,1-a:1,2-c]naphthalene in one pot via autoxidation of the presumed 1,2-di-2-azulenylbenzene derivative. In contrast, a similar reaction of bis(1-methoxycarbonyl-2-azulenyl)acetylene with tetraphenylcyclopentadienone gave the 1,2-di-2-azulenylbenzene derivative. The following cyclodehydrogenation reaction of the benzene derivative with iron(III) chloride afforded diazuleno[2,1-a:1,2-c]naphthalene 6,11-bismethoxycarbonyl derivative. The redox behavior of these novel diazuleno[2,1-a:1,2-c]naphthalenes was examined by cyclic voltammetry (CV). These compounds exhibited two-step oxidation waves at +0.22 to +0.71 V upon CV, which revealed the formation of a radical cation and dication stabilized by the fused two azulene rings under the electrochemical oxidation conditions. Since the 1,2-di-2-azulenylbenzene derivative was oxidized at higher oxidation potentials (+0.83 and +1.86 V), the fusion of the two azulene rings to naphthalene increased electron-donating properties because of the formation of a closed-shell dicationic structure. Formation of the radical cation was characterized by UV-vis spectroscopy under the electrochemical oxidation conditions, although no evidence was obtained for the presumed dication under the conditions of the UV-vis spectroscopy measurement. 相似文献
34.
Kajihara M Sugie T Sano A Fujioka K Urabe Y Tanihara M Imanishi Y 《Chemical & pharmaceutical bulletin》2003,51(1):11-14
Silicone has been utilized as a carrier material for sustained release system of lipophilic drugs. Extensive studies revealed that drug release rate is influenced by factors such as physicochemical properties of the drug and additives.(1-5)) When a lipophilic drug is highly potent at low concentrations, the drug release rate should be strictly controlled so as to avoid side effects. In this study, using vitamin D(3) (VD(3)) as an example of such drugs, we investigated novel method to suppress initial burst and to modify drug release rate from silicone matrix. As a result, it was found that (a). addition of human serum albumin (HSA) suppressed initial burst and enhanced release rate in the later stage, resulting constant release of VD(3), (b). covering a matrix formulation with a membrane of low diffusivity (core-rod formulation) suppressed initial burst and released drug in a constant rate, and (3) using materials for which the drug has high affinity as dissolution solvent (reservoir formulation), the drug release rate was reduced. 相似文献
35.
Methane partial oxidation to formaldehyde with oxygen over SiO2-supported molybdenum oxide catalysts
Hideo Orita Takashi Hayakawa Masao Shimizu Katsuomi Takehira 《Reaction Kinetics and Catalysis Letters》1993,51(1):87-93
The formation rate of formaldehyde increases with increasing surface area of SiO2 support, but the selectivity does not. From the characterization of catalysts using XRD, SEM and Raman spectroscopy, highly dispersed molybdenum oxide was considered to be much more active for the formation of formaldehyde than crystallite forms of MoO3. 相似文献
36.
Masao Kato Yutaka Takemoto Yasuhiko Nakano Masahiro Yamazaki 《Journal of polymer science. Part A, Polymer chemistry》1975,13(8):1901-1910
Some unsaturated monomers bearing hindered phenol and arylamine groups capable of forming stable radicals were prepared. Radical polymerizations of vinyl monomers having such groups were investigated with the use of azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, and tetraethylthiuram disulfide as initiator. Polymerizations of these monomers went normally only when azobisisobutyronitrile was used as initiator. The other initiators inhibited polymerizations remarkably or completely. The results suggest that radicals resulting from benzoyl peroxide and cumene hydroperoxide or tetraethylthiuram disulfide abstract hydrogen of the phenol or the amine to produce the stable radicals, thereby inhibiting the polymerization. Meanwhile, carbon radicals resulting from azobisisobutyronitrile add selectively to the vinyl double bonds of the monomers to initiate the polymerizations. The vinyl derivatives as well as allyl derivatives and cinnamic acid derivatives copolymerize easily with conventional monomers such as styrene, maleic anhydride, and butadiene, again, only when azobisisobutyronitrile was used as initiator. Antioxidative properties for styrene copolymers and butadiene-styrene copolymers incorporating the hindered phenol monomers were investigated. 相似文献
37.
Pavel Smirnov Hisanobu Wakita Masaharu Nomura Toshio Yamaguchi 《Journal of solution chemistry》2004,33(6-7):903-922
The structure and complex formation of concentrated aqueous gallium(III) bromide (GaBr3) solutions have been investigated over a temperature range 80–333 K by Raman spectroscopy, X-ray absorption fine structure (XAFS), and X-ray diffraction. The Raman spectra obtained at various [Br?]/[Ga3+] molar ratios and temperatures have shown that complex formation between Ga3+ and Br? occurs as a predominant species, with [GaBr4]? at [Ga3+] as high as 1~2 M (M = mol?dm ?3) and [Br?]/[Ga3+] ratios > ~2, and that cooling of the solutions favors the formation of the aqua Ga3+. The intermediate species were not seen in the Raman spectra. The XAFS data have revealed that the aqua complex has a sixfold coordination as [Ga(H2O)6]3+ with a Ga3+–H2O distance of (1.96 ± 0.02) Å, whereas the [GaBr4]? complex has a Ga3+–Br? distance of (2.33± 0.02) Å, and that vitrification of the aqueous GaBr3 solution at liquid nitrogen temperature shifts the equilibrium toward the aqua complex. The X-ray diffraction data at different subzero temperatures have shown a tendency of decreasing Ga3+–Br? and increasing Ga3+–H2O interactions with lowering temperature, confirming the preference of aqua Ga3+ in the supercooled liquid state as well as in the glassy state. The Ga3+–H2O distance of ~1.8 Å for the tetrahedral coordination was found in a 2.01 M gallium(III) bromide solution with a [Br?]/[Ga3+] ratio of 3.7 and gradually increased to a value of 1.92 Å for octahedral geometry with decreasing temperature, suggesting that equilibrium shifts from [GaBr4]? to [Ga(H2O)6]3+ through intermediate species, [GaBr n ](3?n)+ (n = 2 and 3). The Ga3+–Br? and Br?–Br? distances within [GaBr4]? with an almost tetrahedral symmetry are (2.35± 0.02) and (3.82± 0.03) Å, respectively. The Ga3+ has the second hydration shell at (4.03± 0.03) Å and the hydration of Br? is characterized with a Br?–H2O distance of (3.35± 0.02) Å at all temperatures investigated. 相似文献
38.
Zhang ZB Fujiki M Motonaga M McKenna CE 《Journal of the American Chemical Society》2003,125(26):7878-7881
The chiral ordering in aggregated poly(3-alkylthiophene) can be controlled by a metal salt-dependent doping-dedoping process. Enhancement or reduction in the chiral anisotropy factor depends on the doping level, such that doping driven by polymer-metal salt interactions, and dedoping driven by aggregate formation must be balanced in order to achieve maximal chiral ordering. This phenomenon provides a new basis to control chiral arrangement in conjugated polymer aggregates, relying solely on doping, and thus avoiding tedious modification of side-chain or main-chain structures. 相似文献
39.
Hiroyuki Ishibashi Motofumi Okada Atsuko Akiyama Kazuyuki Nomura Masazumi Ikeda 《Journal of heterocyclic chemistry》1986,23(4):1163-1166
2,3-Dihydro-5H-1,4-benzoxathiepins were prepared by intramolecular Friedel-Crafts reactions of ethyl α-[2-(aryloxy)ethylthio]-α-chloroacetates or by acid-catalyzed cyclizations of ethyl α-[2-(aryloxy)ethylsulfinyl]-acetate. 1,2,3,5-Tetrahydro-4,1-benzothiazepines were similarly prepared. 相似文献
40.