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971.
The α,β-unsaturated γ,δ-epoxyketone 7 is isomerized almost exclusively to the δ-diketone 9 both upon irradiation in the n → π* absorption band with light of wavelengths above 310 nm (in anhydrous dioxane or benzene solutions) and upon triplet sensitization using acetophenone in benzene. The reaction may be formulated by the cleavage of the Cγ? O oxide bond and the shift of the δ-hydrogen to the γ-position, and thus bears a formal “double bond homology” to the photochemical α,β-epoxyketone rearrangement. Excitation in the π → π* absorption band of 7 with light of wavelength 253,7 nm (in anhydrous dioxane solution) leads to the formation of product 10 as well as to the triplet rearrangement to 9 . With this result a novel partial synthesis of O-acetyl-B-nortestosterone has been accomplished, which has the advantages of fewer steps and higher product yield ( 7 → 10 : ~30% yield) than previously published syntheses. On the basis of the presently available experiments, the mechanism of the transformation 7 → 10 , which constitutes one of the still few examples of enone photoreactions induced selectively from the π,π* excited singlet, remains unknown. 相似文献
972.
V. E. Kuzmin N. S. Novikova T. A. Sidelnikova L. P. Trigub 《Journal of Structural Chemistry》1994,35(4):471-477
The use of topological indices to reveal the relationship between molecular structure and mesomorphous properties is discussed.
Mathematical models for classification of mesophase types are proposed. The effect of molecular structure and attractive ability
on phase transition temperatures is described. Examples of using correlation equations to predict the properties of 2,5-disubstituted
1,3-dioxanes are given.
A. V. Bogatskii Physicochemical Institute, Ukrainian Academy of Sciences. Translated fromZhurnal Struktumoi Khimii, Vol. 35, No. 4, pp. 53–60, July–August, 1994.
Translated by L. Smolina 相似文献
973.
L. N. Koikov E. A. Lisitsa N. A. Alekseeva K. F. Turchin T. Ya. Filipenko 《Chemistry of Heterocyclic Compounds》1992,28(11):1289-1292
3-Ethoxycarbonylquinuclidine obtained by the Grob method is a mixture of 3-ethoxycarbonyl-1-azabicylo-[2.2.2]- and, according to 13C NMR data, 5-ethoxycarbonyl-5-azatricyclo[3.2.1.02,7]octanes (1621). 3-Ethoxy-carbonylquinuclidine was purified by recrystallization of the hydrochloride, hydrolyzed by water to 3-quinuclidinecarboxylic acid, and reduced by LiAlH4 to 3-quinuclidinylmethanol.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, 1509–1512, November, 1992. 相似文献
974.
L. S. Sologub S. D. Moshchitskii T. Ya. Lavrenyuk 《Chemistry of Heterocyclic Compounds》1975,11(1):65-67
The reaction of excess primary aliphatic amines and mercaptans with 2-methyl-3,5,6-trichloro-4-pyridyl vinyl sulfone gives products of addition to the double bond. 相似文献
975.
N. N. Khimich Yu. L. Zub L. A. Koptelova T. S. Mashchenko E. P. Troshina M. G. Voronkov 《Russian Journal of Applied Chemistry》2006,79(11):1769-1774
Sol-gel process of hydrolytic polycondensation of tetramethoxysilane with trimethoxysilyl derivatives of lanthanide phosphoramide
complexes was studied in order to obtain photoluminescent organic-inorganic hybrid materials.
Original Russian Text N.N. Khimich, Yu.L. Zub, L.A. Koptelova, T.S. Mashchenko, E.P. Troshina, M.G. Voronkov, 2006, published
in Zhurnal Prikladnoi Khimii, 2006, Vol. 79, No. 11, pp. 1789–1794. 相似文献
976.
The cyclization of 2-(1-alkynyl)-2-alken-1-ones 1 proceeded very smoothly in the presence of alcohols 2 with a catalytic amount of Cu(I)Br in DMF at 80 degrees C, leading to the formation of highly substituted furans 3. The catalytic system reported herein is easy to handle, compared to the previously known system wherein the reaction between 1 and 2 needed to use moisture sensitive gold(III) chloride. 相似文献
977.
The acceleration of the electrodeposition and anodic dissolution of copper in acid sulfate solutions, caused by sodium pyrophosphate, is found to be due to a chemical heterogeneous stage, which involves an adsorbed pyrophosphate ion (probably, H2P2O7
2–). The assumption about the presence of a surface complex on the surface of copper is substantiated. As follows from adsorption isotherms, obtained for strongly acid (to 2 M H2SO4) solutions from anodic Tafel plots, the effect of the acid concentration on the rate of the discharge–ionization of copper is caused by its effect on the surface coverage by the adsorbate. Measurements of the quasi-equilibrium potential of the freshly renewed surface of copper confirm the assumption about the inhibiting of the surface diffusion of adsorbed atoms by adsorbed pyrophosphate. 相似文献
978.
T. I. Vakul'skaya L. I. Larina O. B. Nefedova V. A. Lopyrev 《Chemistry of Heterocyclic Compounds》1982,18(4):400-404
The results of an EPR investigation are presented with polarographs of electrochemical excitation of nitropyrazoles in acetonitrile. It is shown that 3- and 4-nitropyrazoles are excited in two single-electron stages with formation of dianion radicals. Upon excitation, N-alkylnitropyrazoles form stable anion radicals. 1-Nitro- and 1,4-dinitropyrazoles are excited upon splitting off of the NO2 anion. Excitation potentials of the nitropyrazoles and hyperfine interaction constants for the corresponding ion radicals are given.See [1] for Communication 2.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 523–527, April, 1982. 相似文献
979.
Simultaneous determination of cefazolin in rat blood and brain by microdialysis and microbore liquid chromatography 总被引:3,自引:0,他引:3
A sensitive microbore liquid chromatographic method combined with the minimally invasive technique of microdialysis was devised for simultaneously and continuously monitoring the levels of unbound blood and brain cefazolin in rats. Microdialysis probes were inserted into the jugular vein and brain striatum for blood and brain sampling, respectively. Chromatographic conditions consisted of a mobile phase of methanol-acetonitrile-100 mM monosodium phosphoric acid (20:10:70, v/v, pH 4.5) pumped through a microbore reversed-phase column at a flow rate of 0.05 mL/min. The ultraviolet detection wavelength was set at 270 nm. An on-line design allowed direct and continuous analysis of protein-free samples in the dialysate. Microdialysis probes, being home-made, were screened for acceptable in vivo recovery. Chromatographic resolution and detection were validated for response linearity as well as intra-day and inter-day variabilities. This method was then applied to pharmacokinetic profiling of protein unbound cefazolin in both the blood and brain following intravenous administration (10 mg/kg, i.v., n = 6). Rapid appearance of cefazolin in the rat brain striatal dialysate following drug injection suggested good blood-brain barrier penetration. According to a non-compartmental pharmacokinetics model, the area under the concentration (AUC) vs time ratio of cefazolin in rat brain and blood was 6%. 相似文献
980.
Protein profiling of rat cerebella during development 总被引:7,自引:0,他引:7
Protein profiles of developing rat cerebella were analyzed by means of two-dimensional gel electrophoresis (2-DE) and mass spectrometry (MS). The analysis of adult rat cerebellum gave rise to a protein map comprising approximately 3000 spots detectable by silver staining following high resolution 2-DE with a pH range of 3-10 and a mass range of 8-100 kDa. To obtain landmarks for comparison of developmental profiles of cerebellar proteins, 100 spots were subjected to peptide mass fingerprinting using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS), and 67 spots were assigned on the map. Analysis of profiles of the developing cerebella revealed significant changes in the expression of proteins during development. In most cases the expression levels of proteins increased as the cerebellum matured, while the expression of 42 spots appeared specific or remarkably abundant in the immature cerebellum. Peptide mass fingerprinting of these spots allowed us to identify 29 proteins, which include, in addition to proteins of unknown function, many proteins known to have roles in the development of the central nervous system. These results suggest that the proteomic approach is valuable for mass identification of proteins involved in cerebellar morphogenesis. 相似文献