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991.
The UV.-isomerisation of 11-oxo-14β,17α-pregnane 9 to the 11,19-cyclo-derivative 11 is described. In addition the Pb(OAc)4-fragmentation of photoproduct 11 was investigated. 11 yielded besides the expected 11-oxo-19-hydroxy-pregnane 18 the novel 9,11-seco-11,19-cyclosteroid 19 . The structure of 19 was established by chemical transformations and subsequently confirmed by X-ray analysis [2]. 相似文献
992.
On irradiation with Pyrex-filtered light, 5-bromo-1,3-dimethyluracil 1 coupled with methyl- and methoxynaphthalenes 2–7 to give 5-naphthyl-1,3-dimethyluracils 8–13. No coupling product was formed by triplet sensitization except in the cases of 2,3-dimethioxynaphthalene 3 and 2-methoxynaphthalene 5. indicating that the singlet excited states of the naphthalenes are involved in the unsensitized coupling reaction. The kqτ values of the fluorescence quenching of 1,4-dimethoxynaphthalene 2 and 1-methoxynaphthalene 4 by 1 in acetonitrile were comparable with those obtained from the kinetics of the coupling reactions. On the basis of this fact and the fluorescence-quenching rate constants kq in acetonitrile ranging from 108 to 109 M?1 sec?1, involvement of an electron-transfer process possibly via a singlet exciplex is proposed for this cross-coupling reaction. 相似文献
993.
Y. Saito Y. Miyamoto M. Magara S. Sakurai S. Usuda 《Journal of Radioanalytical and Nuclear Chemistry》2003,255(2):341-345
In order to examine the feasibility of the adsorbed compounds on the pine needles for environmental monitoring of uranium, the adsorbed compounds were recovered by solvent washing, and the elemental concentrations in the compounds were compared with those of air particles and pine needles. It was found, that the concentration patterns of elements in the compounds corresponded to those of air particles, which meant that the air particles were the main components of the compounds. The analysis by ICP-MS suggested that the uranium in the compounds has a natural composition. Therefore, the adsorbed compounds to the pine needles can be considered as potential indicators for the environmental monitoring of uranium. 相似文献
994.
Kobayashi S Matsubara R Nakamura Y Kitagawa H Sugiura M 《Journal of the American Chemical Society》2003,125(9):2507-2515
In the presence of a catalytic amount of Cu(OTf)(2)-chiral diamine 3e complex, N-acylimino esters reacted with silyl enol ethers to afford the corresponding Mannich-type adducts in high yields with high enantioselectivities. A wide variety of silyl enol ethers derived from ketones, as well as esters and thioesters, reacted smoothly. In the reactions of alpha-substituted silyl enol ethers (alpha-methyl or benzyloxy), the desired syn-adducts were obtained in high yields with high diastereo- and enantioselectivities. Several intermediates for the synthesis of biologically important compounds were prepared using this novel catalytic asymmetric Mannich-type reaction, and at the same time, absolute and relative stereochemical assignments were made. In addition, it has been revealed that alkyl vinyl ethers reacted with N-acylimino esters in the presence of a catalytic amount of the Cu(II) catalyst to give the corresponding Mannich-type adducts in high yields with high enantioselectivities. This is the first example of catalytic asymmetric Mannich-type reactions with alkyl vinyl ethers. The reaction mechanism, structure of chiral catalyst-electrophile complexes, and transition states of these catalytic asymmetric reactions were assumed based on X-ray crystallographic analysis of the Cu(II)-chiral amine complex, PM3 calculations, and FT-IR analyses, etc. Finally, (1R,3R)-N-(3-hydroxy-1-hydroxymethyl-3-phenylpropyl)dodecanamide (HPA-12, 1), a new inhibitor of ceramide trafficking from endoplasmic reticulum to the site of sphingomyerin (SM) synthesis, has been synthesized efficiently using the present Mannich-type reaction as a key step. The synthesis involved three steps (two-pot), and total yield was 82.9%. 相似文献
995.
Kobori A Horie S Suda H Saito I Nakatani K 《Journal of the American Chemical Society》2004,126(2):557-562
We have synthesized the first surface plasmon resonance (SPR) sensor that detects cytosine-cytosine (C[bond]C) mismatches in duplex DNA by immobilizing aminonaphthyridine dimer on the gold surface. The ligand consisting of two 2-aminonaphthyridine chromophores and an alkyl linker connecting them strongly stabilized the C[bond]C mismatches regardless of the flanking sequences. The fully matched duplexes were not stabilized at all under the same conditions. The C[bond]T, C[bond]A, and T[bond]T mismatches were also stabilized with a reduced efficiency. SPR analyses of mismatch-containing 27-mer duplexes were performed with the sensor surface on which the aminonaphthyridine dimer was immobilized. The response for the C[bond]C mismatch in 5'-GCC-3'/3'-CCG-5' was about 83 times stronger than that obtained for the fully matched duplex. The sensor successfully detects the C[bond]C mismatch at the concentration of 10 nM. SPR responses are proportional to the concentration of the C[bond]C mismatch in a range up to 200 nM. Aminonaphthyridine dimer could bind strongly to the C[bond]C mismatches having 10 possible flanking sequences with association constants in the order of 10(6) M(-1). The facile protonation of 2-aminonaphthyridine chromophore at pH 7 producing the hydrogen-bonding surface complementary to that of cytosine was most likely due to the remarkably high selectivity of 1 to the C[bond]C mismatch. 相似文献
996.
Liquid chromatography on columns with small internal diameters has been reviewed as the intermediate technique between conventional liquid chromatography and microchip separations. The development of micro column separations in the early years has been described, starting with the papers of Horváth and co-workers and Ishii and co-workers, continuing into the first part of the eighties, then making a leap in time to recent innovations with small-bore columns. Based on internal diameters a classification of the different analytical HPLC columns has been suggested. The advantages of small-bore columns have been discussed, with particular emphasis on the advantage of coupling to concentration sensitive detectors when the sample amount is limited. Open tubular columns are treated as a part of the historic background. The recent developments include a brief look into the current status of monolithic columns, the use of packed nano columns and micro columns with electrospray mass spectrometry, and the potential of two-dimensional comprehensive liquid chromatography. Finally, the coupling of sample preparation to analytical columns and the future applications of the novel technological improvements to the microchip separation methods have been discussed. 相似文献
997.
Y. Sakai H. Saito T. Sodesawa F. Nozaki 《Reaction Kinetics and Catalysis Letters》1984,24(3-4):253-257
The catalytic reaction between hydrocarbons and carbon dioxide, e.g. CH4+ +CO22CO+2H2 and C6H6CH3+CO2C6H6+2CO+H2, has been investigated over various metallic catalysts under atmospheric pressure. In general, Rh–Al2O3 catalyst was found to be excellent in activity and selectivity. The reaction rates were moderately dependent on the pressure of carbon dioxide, whereas it was little influenced by the pressure of hydrocarbon.
, ., CH4+CO22CO+2H2 C6H5CH3+CO2C6H6+2CO+X2, . , Rh–Al2O3 . , .相似文献
998.
K. Jinno H. Matsui H. Ohta Y. Saito K. Nakagawa H. Nagashima K. Itoh 《Chromatographia》1995,41(5-6):353-360
Summary Two-step liquid chromatographic separation (LC) has been applied to soot extract and the identification of higher fullerenes
has been accomplished by LC-MS measurements using an ESI interface. The first separation step is preparative-scale LC using
a 50 mm i.d. column packed with monomeric octadecylisilica (ODS) because elution is mainly controlled by relative molecular
mass. 39 batches of five fractions each were collected and then as the second separation step each fraction was analysed by
analytical-scale LC using a conventional column of a polymeric ODS phase which can elute fullerenes according to shape and
structure. This stationary phase can also separate many isomers of higher fullerenes, consequently the existence of several
higher fullerenes larger than C86 has been confirmed and their UV-Vis spectra were obtained by the photodiode array detection system coupled to the analytical
LC. 相似文献
999.
Sato J Saito N Yamada Y Maeda K Takata T Kondo JN Hara M Kobayashi H Domen K Inoue Y 《Journal of the American Chemical Society》2005,127(12):4150-4151
Germanium nitride beta-Ge3N4 dispersed with RuO2 nanoparticles is presented as the first example of a non-oxide photocatalyst for the stoichiometric decomposition of H2O into H2 and O2. All of the successful photocatalysts developed for overall water splitting over the past 30 years have been based on oxides of metals. The discovery of a non-oxide photocatalyst, such as nitrides and oxynitrides, achieving the same function is therefore expected to stimulate research on non-oxide photocatalysts. New opportunities for progress in the development of visible light-driven photocatalysis can thus be expected, as the higher valence band positions of metal nitrides compared to the corresponding metal oxides provide narrower band gaps, which are suitable for visible light activity. 相似文献
1000.
[reaction: see text] A novel method for synthesizing 4-acetoxy-2-amino-3-arylbenzofurans (4) from 1-aryl-2-nitroethylenes (1) and cyclohexane-1,3-diones (2) is described. The method features one-pot operation of a solution of 1 and 2 in THF with catalytic Et3N (rt, 12 h) followed with Ac2O, Et3N, and DMAP (rt, 5 h), although the process consists of 13 elementary reactions. 相似文献