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排序方式: 共有217条查询结果,搜索用时 15 毫秒
91.
Haru Ogawa Hiroshi Morita Satoko Suemura Taiji Imoto Yasuyoshi Nogami Toshitaka Koga Yujiro Sakuragi Izumi Miyamoto Hidefumi Kato Yōichi Taniguchi 《Tetrahedron letters》1985,26(45):5567-5570
The titled annulenone 1 could be converted into new annulenones 3 and 8 by carbonyl transposition reactions. Compound 8 can be regarded as the first 14π hydroxy-enone as a higher homolog of tropolone (6π) and hydroxy[11]annulenones (10π), and was proved to be aromatic. 相似文献
92.
Hidefumi Hirai Makoto Komiyama 《Journal of polymer science. Part A, Polymer chemistry》1974,12(12):2701-2719
The equilibrium constants for the complex formation between stannic chloride and methyl methacrylate were determined in n-hexane–toluene solution at 0, ?20, and ?30°C by using the absorption band at 350 nm. Continuous variation plots at ?20°C in n-hexane based on the 1H-chemical shifts definitely show a 1:1 interaction between the coordinated methyl methacrylate and styrene or toluene. The magnitudes of the shifts for the four groups of protons in methyl methacrylate are found to be in a specific ratio in common with the 1:2 complex–styrene or -toluene system. The equilibrium constants for the ternary molecular complex formation between the 1:2 complex and styrene or toluene were determined in n-hexane in the temperature range ?50 to +20°C by use of the chemical shifts. The concentrations of the complex species in the alternating copolymerization solutions were estimated by use of the equilibrium constants. There is a linear relationship between the enthalpy and the entropy changes for the ternary molecular complex formation, which is governed by the enthalpy factor. The specificity of the interactions indicates a specific time-averaged orientation of benzene ring to the coordinated methyl methacrylate. The effects of the coordination of methyl methacrylate to stannic chloride were discussed on the basis of results of 13C-NMR spectroscopy. 相似文献
93.
Tarui N Nakahama K Nagano Y Izawa M Matsumoto K Kori M Nagata T Miki T Yukimasa H 《Chemical & pharmaceutical bulletin》2002,50(1):59-65
Microbial enantioselective ester hydrolysis for the preparation of optically active (3R,5S)-(-)-5-phenyl-4,1-benzoxazepine-3-acetic acid derivatives as potent squalene synthase inhibitors was investigated. Pseudomonas diminuta and Pseudomonas taetrolens hydrolyzed the racemic ethyl ester of the 5-(2-chlorophenyl) analogue to yield the (-)-carboxylic acid with excellent enantiomeric excess (>99% ee). We found that the (-)-enantiomer was an active inhibitor. Bulkiness of the ester moiety did not affect the enantioselectivity but did affect reactivity. The racemic ethyl ester of the 5-(2-methoxyphenyl) analogue, 5-(2,3-dimethoxyphenyl) analogue and 5-(2,4-dimethoxyphenyl) analogue were also hydrolyzed with Pseudomonas taetrolens to afford enantiomerically pure (-)-carboxylic acids in large scale. As another route to (3R,5S)-(-)-7-chloro-5-(2,3-dimethoxyphenyl)-1-neopentyl-2-oxo-1,2,3,5-tetrahydro-4,1-benzoxazepine-3-acetic acid [(-)-1c], the earlier intermediate (-)-2-amino-5-chloro-alpha-(2,3-dimethoxyphenyl)benzyl alcohol [(-)-12] was successfully obtained by asymmetric hydrolysis of (+/-)-5-chloro-alpha-(2,3-dimethoxyphenyl)-2-pivaloylaminobenzyl acetate with Pseudomonas sp. S-13 with >99% ee in kilogram scale followed by alkaline treatment. The product (-)-12 was converted to (-)-1c without racemization. 相似文献
94.
Seki S Koizumi Y Kawaguchi T Habara H Tagawa S 《Journal of the American Chemical Society》2004,126(11):3521-3528
The transient absorption of radical cations of a variety of substituted polysilanes is discussed quantitatively in terms of the molar extinction coefficient and oscillator strength by nanosecond pulse radiolysis. Oxygen-saturated polysilane solutions in benzene exhibit a strong transient absorption band ascribed to the polysilane radical cation. The transient species react with N,N,N',N'-tetramethyl-p-phenylene-diamine (TMPD) to produce TMPD radical cations. On the basis of the molar extinction coefficient of the TMPD radical cation, the molar extinction coefficients for the radical cations of polysilanes are found to increase in the range 3.3 x 10(4) to 2.0 x 10(5) M(-)(1) cm(-)(1) with increasing polymer segment length. The stepwise increase in the total oscillator strength with an increase in the number of phenyl rings directly bonded to the Si skeleton suggests the delocalization of the positive polaron state and/or the SOMO state over the phenyl rings, indicating the importance of phenyl rings in intermolecular hole transfer processes. 相似文献
95.
Tze-Loon Neoh Hidefumi Yoshii Takeshi Furuta 《Journal of inclusion phenomena and macrocyclic chemistry》2006,56(1-2):125-133
Encapsulation and release of carbon dioxide (CO2) into and from α-cyclodextrin (α-CD) was studied. Initial moisture content of α-CD and CO2 pressure were found to have affected the encapsulation behavior. The increase of CO2 pressure has constantly accelerated the encapsulation rates and increased the maximum inclusion ratio, whereas the increase of initial moisture content showed no consistent effect. The saturated α-CD solution produced the inclusion complex crystal of similar inclusion ratio to solid α-CD. The release characteristics of inclusion complexes were also monitored at various relative humidities at 25 °C. Predominantly, increase in storage humidity accelerated the release of CO2. The inclusion complex crystal prepared from saturated α-CD solution showed the most stable release characteristic at all storage humidities investigated. The encapsulation and the release characteristics were analyzed using the first-order reaction equation and the Avrami’s equation respectively, in order to estimate the rate processes of encapsulation and release. The FT-IR spectra of inclusion complexes presented an absorption band at wavenumber around 2338 cm−1, indicating CO2 molecules resided inside the α-CD cavities in gaseous state rather than being bound to the hydroxyl groups of α-CD. Powder X-ray diffractometry was carried out to investigate the crystal lattice structure of α-CD and inclusion complexes. Scanning electron microscopy was also performed for morphological examination. 相似文献
96.
Naoto Kondo Kunio Imai Minoru Isobe Toshio Goto Akira Murasugi Chiaki Wada-Nakagawa Yukimasa Hayashi 《Tetrahedron letters》1984,25(35):3869-3872
The unit peptide, cadystin, of the cadmium-binding peptides occurring in a fission yeast was further separated into two major components, cadystin A and B, structures of which were determined to be 1 and 2, respectively, and confirmed by synthesis. The structure previously reported for cadystin was thus revised. 相似文献
97.
Hidefumi Hirai Kazuhiko Takeuchi Makoto Komiyama 《Journal of polymer science. Part A, Polymer chemistry》1982,20(1):159-172
Alternating copolymerizations of methyl methacrylate with styrene in the presence of boron trichloride at 0°C in 1,2-dichloroethane were carried out by using benzoyl peroxide as an initiator. Conversion increased proportionally with polymerization time, whereas the degree of polymerization was constant irrespective of time. The rate depended linearly on the square root of the concentration of benzoyl peroxide. The equilibrium constants for the formation of the ternary molecular complex composed of methyl methacrylate, styrene, and boron trichloride in 1,2-dichloroethane at ?20, ?10, and +4°C were determined by 1H-NMR spectroscopy. The concentrations of the ternary molecular complex in the polymerization mixtures were evaluated from the equilibrium constant of the formation. The rate of the alternating copolymerization was proportional to the first order of the concentration of the ternary molecular complex. The distribution of methyl methacrylate-centered triads in the alternating copolymer was different from that of styrene-centered triads. These results can be explained by a mechanism involving the homopolymerization of a ternary molecular complex. 相似文献
98.
Kota Sato Tatsuo Goto Susumu Iwabuchi Hidefumi Hirai 《Journal of polymer science. Part A, Polymer chemistry》1993,31(3):763-768
The geometrical and electronic structures of the binary radical complexes of 2-methoxycarbonyl propyl radical with boron trichloride and with boron trifluoride were determined by using an ab initio molecular orbital method. The 2-methoxycarbonyl propyl radical complex was a model of the growing radical end in the copolymerization of methyl methacrylate in the presence of boron halides. The most stable structure of the binary radical complex composed of 2-methoxycarbonyl propyl radical with boron trichloride was a twisted form in which the dihedral angle between the vinyl group and the ester group was 32°, while that of the binary radical complex composed of methyl methacrylate radical with boron trifluoride was a planar form as the free radical. The frontier orbital energy of 2-methoxycarbonyl propyl radical was lowered by 0.06 au by the coordination of boron trichloride, while that was lowered only by 0.02 au by the coordination of boron trifluoride. The polymerization mechanism was elucidated on the basis of these predictions. © 1993 John Wiley & Sons, Inc. 相似文献
99.
Hidefumi Hirai 《Journal of inclusion phenomena and macrocyclic chemistry》1984,2(3-4):455-466
Selective formylation of phenol at the 4-position is achieved by using -cyclodextrin as catalyst in the reaction of phenol with chloroform in aqueous alkali. The reactions of 1,3-dihydroxybenzene and indol, respectively, in the place of phenol give 2,4-dihydroxybenz-aldehyde and indole-3-aldehyde in virtually 100% selectivies and high yields. The reactions of para-substituted phenols, 4-methylphenol and 5,6,7,8-tetrahydro-2-naphthol, instead of phenol, effect the selective dichloromethylation at the para-positions. Selective carboxylation of phenol at the 4-position is achieved in the reaction of phenol with carbon tetrachloride in aqueous alkali by using -cyclodextrin and copper powder as catalyst.The reaction of 2,4,6-trimethylphenol and allyl bromide in aqueous alkali using hexa-N-methylformamido--cyclodextrin as catalyst yields 4-allyl-2,4,6-trimethyl-2,5-cyclohexadienone in high selectivity.The structure of the ternary inclusion complex composed of -cyclodextrin, phenol, and, chloroform or carbon tetrachloride, formed in the reaction mixture, is determined by NMR spectroscopy. The selective catalysis by cyclodextrin was attributed to the regulation of molecular conformation of substrates with respect to dichlorocarbene, to trichloromethyl cation, or to allyl cation in the ternary molecular complex. 相似文献
100.
A convergent synthesis of two possible diastereomers of reticulatain-1 (1a and 1b) was accomplished. Comparison of the specific optical rotations of 1a and 1b did not allow for the strict determination of the absolute configuration. However, bis-(R)-MTPA esters of 1a and 1b showed a clear difference in chemical shifts in the 1H NMR spectra. If the bis-(R)-MTPA ester of natural reticulatain-1 (1) is available, the absolute configuration of 1 will be determined. Inhibitory action of these compounds was examined with bovine heart mitochondrial complex I. Both compounds showed almost the same activity. 相似文献