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81.
Kazuhiro Kobayashi Atsushi Takanohashi Kenichi Hashimoto Osamu Morikawa Hisatoshi Konishi 《Tetrahedron》2006,62(44):10379-10382
A facile synthetic method for 4,5-diaminopyrrolo[1,2-a]quinoline derivatives has been developed. Treatment of 2-(pyrrol-1-yl)benzaldehydes with secondary amine hydrochloride/NaI/TMSCl/Et3N in the presence of an isocyano compound leads to the formation of 4-alkyl(or aryl)amino-5-dialkylaminopyrrolo[1,2-a]quinolines. 相似文献
82.
Kakinoki K Yamane K Yamamoto M Teraoka R Sugimoto I Matsuda Y 《Chemical & pharmaceutical bulletin》2005,53(9):1092-1096
TiO(2) has been widely used in pharmaceutical products, and it also has been used as a photocatalyst. In this study, the influence of photocatalytic activity on the stability of solid-state mequitazine, an H(1)-blocker, was investigated. The photo-degradation of mequitazine with TiO(2) occurred under irradiation with both light sources. The degree of degradation of mequitazine with anatase was higher than that of rutile. The degradation was significantly enhanced with increasing relative humidity. The relationship between the apparent degradation rate constant and water vapor pressure could be clearly described by a simple power law. The major photo-degradation products of mequitazine, resulting from photocatalytic activity of TiO(2), were mequitazine-S-oxide and mequitazine-sulphone. A remarkable degradation of mequitadine occurred with addition of TiO(2), and its photocatalytic activity was controlled by water vapor pressure. The photo-degradation of mequitazine with TiO(2) is a different process from mequitazine without TiO(2), because mequitazine-S-oxide and mequitazine-sulphone are not formed with normal photo-degradation of mequitazine. 相似文献
83.
Yamamoto Y Hattori R Miwa T Nakagai YI Kubota T Yamamoto C Okamoto Y Itoh K 《The Journal of organic chemistry》2001,66(11):3865-3870
A monomeric titanocene(III) derivative, Cp(2)TiPh, effectively promoted the pinacol coupling of both an aromatic aldehyde, benzaldehyde, and an aliphatic aldehyde, 3-phenylpropionaldehyde. The same reactive complex was successfully generated by a catalytic amount of a precursor, Cp(2)Ti(Ph)Cl, and its stoichiometric amount of Zn. The Cp(2)TiPh-catalyzed pinacol coupling of benzaldehyde derivatives and aliphatic aldehydes afforded the corresponding 1,2-diols in high yields with moderate to good threo-selectivity. On the other hand, Cp(2)TiPh-catalyzed pinacol cyclization of dials gave cyclic 1,2-diols with excellent diastereoselectivity. The extension of this protocol to chiral dials demonstrated that the phenyltitanium complex catalytically transmitted an axial chirality or a central chirality of the starting dials to the central chirality of the resultant 1,2-diols. 相似文献
84.
9,10-Dihydro-4,5-dimethylphenanthrene has two rotational isomers around the pivot bond. This compound shows a complex signal pattern of an AA′BB′ type for the four methylene protons in the NMR spectrum. The inversion process is analysed using the density matrix method, and at various temperatures the calculated line shapes are fitted to the observed spectra to obtain the life-time τ of the inversion. From the logarithmic plot of the life time versus 1/T, the kinetic parameters of this intramolecular inversion process are obtained as follows: Ea = 25·3 ± 1·0 Kcal/mole ΔG3 = 24°1 ± 1·0 Kcal/mole at 25·0° ΔH3 = 24·7 ± 1·0 Kcal/mole ΔS3 = 2·1 ± 0·8 e.u. 相似文献
85.
A rhenium complex, [ReBr(CO)3(thf)]2, catalyzes the reaction of an aromatic aldimine with an acetylene to give an indene derivative in a quantitative yield. The reaction proceeds via C-H bond activation, insertion of the acetylene, intramolecular nucleophilic cyclization, and reductive elimination. In contrast to ruthenium and rhodium catalysts, which are usually employed in this type of reaction, the rhenium catalyst promotes the intramolecular nucleophilic cyclization of the alkenylmetal species generated by insertion of the acetylene. 相似文献
86.
A microanalytical method for the measurement of selenium in waters and biological materials by a flameless atomic-absorption technique has been developed. The ammonium pyrrolidinedithiocarbamate-methyl isobutyl ketone extraction system is used for separation from interfering materials such as large amounts of alkali and alkaline earth metal salts and mineral acids. The atomic-absorption sensitivity for selenium is found to be enhanced to a large extent by co-extraction of some transition metal ions. Copper(II) has been used successfully as such an additive to diminish the volatility of selenium in the graphite furnace during the ashing step of the atomization cycle. When the aqueous phase/organic solvent volume ratio is 5 and the volume injected into the graphite furnace is 20 mul, the sensitivity for selenium is 0.3 ng/ml for 1% absorption. The relative standard deviation is ca. 2%. Interference by other metal ions is prevented by masking with EDTA. The method has been applied satisfactorily for the determination of minute amounts of selenium in waters and various biological materials. 相似文献
87.
D. J. Assinder M. Yamamoto C. K. Kim R. Seki Y. Takaku Y. Yamauchi S. Igarashi K. Komura K. Ueno 《Journal of Radioanalytical and Nuclear Chemistry》1993,170(2):333-346
A survey has been carried out of40K,60Co,99Tc,106Ru,125Sb,129I,134Cs,137Cs,154Eu,226Ra,228Ra,237Np,238Pu,239,240Pu,241Pu,241Am,242Cm, and243,244Cm activities in sediments from the Irish Sea. Several of these radionuclides were measured independently at two separate laboratories to enable the intercomparison of the results produced. The comprehensive data set generated allows the present spatial distributions of these radionuclides in coastal sediments to be examined in relation to sediment textural characteristics and by comparison with earlier survey, enables the temporal trends in their activities to be determined. In general all artificial radionuclides showed lower activities in sediments in response to falling discharges from Sellafield and relationships with either grain size, distance from Sellafield or both. Isotope ratios were similar to cumulative weighted activity ratios rather than present day values due to sediment mixing. Pu levels supplied evidence for the lag in response of sediment deposits with increasing distance from Sellafield due to sediment transport. 相似文献
88.
M. Sakanoue M. Yamamoto K. Komura 《Journal of Radioanalytical and Nuclear Chemistry》1987,115(1):71-82
Low-energy photon spectrometry with -spectrometry was used to determine the environmental concentrations of low-level actinides and other nuclides, especially210Pb and210Po. The isotopic ratio of240Pu/239Pu was successfully determined by measuring Lx-ray/-ray counting ratio. A reliable method has been developed for the determination of extremely low-level237Np global fallout in environmental samples. The non-destructive determination by Ge-LEPS for natural210Pb in various samples (tobacco leaves, commercially available tobacco, etc.) was also carried out with the determination of210Po by -spectrometry using209Po as a yield tracer. 相似文献
89.
Ono K Yoshida A Saito N Fujishima T Honzawa S Suhara Y Kishimoto S Sugiura T Waku K Takayama H Kittaka A 《The Journal of organic chemistry》2003,68(19):7407-7415
Six novel 2-substituted analogues of 1alpha,25-dihydroxy-19-norvitamin D(3), 6a,b-8a,b, were efficiently synthesized utilizing (-)-quinic acid as the A-ring precursor. The C2-modified A-rings were prepared as 4-alkylated (3R,5R)-3,5-dihydroxycyclohexanones 12-15 from (-)-quinic acid based on radical allylation at the C4 position of methyl (-)-quinicate. The new type of the CD-ring coupling partner 23 was synthesized from 25-hydroxy Grundmann's ketone 19 to apply to the modified Julia olefination to construct a diene unit between the A-ring and the CD-ring. The coupling yields, including a deprotection step, were 47-62%. After the separation of the diastereomers based on C2 stereochemistry, the structure (2alpha or 2beta) was determined by (1)H NMR experiments and compared to DeLuca's 2-methyl- and 2-ethyl-1alpha,25-dihydroxy-19-norvitamin D(3). Thus, the synthesized 2alpha-(3-hydroxypropyl)-1alpha,25-dihydroxy-19-norvitamin D(3) (8a) showed almost the same potency in binding to the bovine thymus vitamin D receptor (VDR) as the natural hormone 1, while its beta-isomer 8b had only a 3% affinity. Both 2alpha-allyl- and 2alpha-propyl-1alpha,25-dihydroxy-19-norvitamin D(3) (6a and 7a) and their 2beta-analogues (6b and 7b) possessed a weak affinity for the VDR. The strong VDR ligand 8a was ca. 36-fold more potent in induction of HL-60 cell differentiation than 1, and interestingly, even the weaker ligand 8b showed a 6.7-fold higher potency in the cell differentiation activity than that of 1. 相似文献
90.
A new class of chiral ligand, tethered bis(8-quinolinol) (TBOxH), is developed. Its chromium complex, TBOxCrCl (3 mol %), effectively catalyzes the pinacol coupling reaction of aromatic aldehydes at room temperature with high yield (up to 94%), high diastereoselectivity (up to dl:meso = 98:2), and high enantioselectivity (up to 98%). The scope of the present method turns out not to be limited to aromatic aldehyde derivatives, as cyclohexanecarboxaldehyde undergoes pinacolization as well (44% yield, dl:meso = 93:7, 84% ee). The method provides an efficient access to enantioenriched 1,2-diols. 相似文献