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781.
1,4-Dicarbonyl derivatives of glycosides are produced by ozonolysis or Wacker oxidation. A stable ozonide is isolated and a carbonyl group reduced whilst maintaining the ozonide functionality. The 1,4-dicarbonyl compounds are converted to various N-substituted pyrrolidines by diastereoselective double reductive amination The resulting aza-heteroannulated sugars no significant inhibition of any glycosidase, with the exception of compound 12g, which is a weak inhibitor of β-galactosidase. 相似文献
782.
Dr. Siew‐Peng Chia Dr. Emma Carter Dr. Hong‐Wei Xi Dr. Yongxin Li Dr. Cheuk‐Wai So 《Angewandte Chemie (International ed. in English)》2014,53(32):8455-8458
The two‐electron reduction of a Group 14‐element(I) complex [RË?] (E=Ge, R=supporting ligand) to form a novel low‐valent dianion radical with the composition [RË:]. 2? is reported. The reaction of [LGeCl] ( 1 , L=2,6‐(CH?NAr)2C6H3, Ar=2,6‐iPr2C6H3) with excess calcium in THF at room temperature afforded the germylidenediide dianion radical complex [LGe]. 2??Ca(THF)32+ ( 2 ). The reaction proceeds through the formation of the germanium(I) radical [LGe?], which then undergoes a two‐electron reduction with calcium to form 2 . EPR spectroscopy, X‐ray crystallography, and theoretical studies show that the germanium center in 2 has two lone pairs of electrons and the radical is delocalized over the germanium‐containing heterocycle. In contrast, the magnesium derivative of the germylidendiide dianion radical is unstable and undergoes dimerization with concurrent dearomatization to form the germylidenide anion complex [C6H3‐2‐{C(H)?NAr}Ge‐Mg‐6‐{C(H)‐NAr}]2 ( 3 ). 相似文献
783.
Emma H. Chukhajian Martiros K. Nalbandyan Hasmik R. Gevorkyan Eliza H. Chukhajian Henrik A. Panosyan Armen G. Ayvazyan Rafael A. Tamazyan 《Journal of heterocyclic chemistry》2008,45(3):687-692
Dialkylpropyn‐1‐yl(or allyl)(3‐isopropenylpropyn‐2‐yl)ammonium bromides under base‐catalyzed condition instantly undergo intramolecular cyclization. The cyclization of dialkylpropyn‐1‐yl(3‐isopropenylpropyn‐2‐yl)ammonium bromides leads to the formation of 2,2‐dialkyl‐5‐methylisoindolinium salts. In case of allyl analogs, instead of the expected 2,2‐dialkyl‐6‐methyl‐3a,4‐dihydroisoindolinium salts their isomeric forms ‐ 2,2‐dialkyl‐5‐methyl‐2,6,7,7a‐tetrahydro‐1H‐isoindolium bromides are obtained. In alkaline medium they are transform into the dihydroisoindolinium salts, the cleavage of which in two directions ‐ 1,2 and 1,6 leads to the mixture of isomeric dialkyl‐1,4‐dimethyl‐ and 2,4‐dimethylbenzyl‐amines. Study of the behavior of 2,2‐dialkyl‐5‐methylisoindolinium salts under conditions of water‐base cleavage showed, that only spiro[5‐methylisoindolyn]morpholinium bromide undergoes 1,2‐elimination, forming 5‐methylisoindoline 2‐vinyl ethyl ester. 相似文献
784.
Kristensen EM Nederberg F Rensmo H Bowden T Hilborn J Siegbahn H 《Langmuir : the ACS journal of surfaces and colloids》2006,22(23):9651-9657
The structure of a biomimetic phosphorylcholine (PC)-functionalized poly(trimethylene carbonate) (PC-PTMC-PC), linked to a silicon substrate through an aminolysis reaction at 120 degrees C with (3-aminopropyl)trimethoxysilane (APTMS), was studied using photoelectron spectroscopy. Two chemical states were found for the unreacted APTMS amine, a neutral state and a protonated state, where the protonated amine on average was situated closer to the silicon substrate than the neutral amine. The experiments also indicated the presence of a third chemical state, where amines interact with unreacted silanol groups. The PTMC chains of the grafted films were found to consist of only 2-3 repeat units, with the grafted chains enriched in the zwitterionic end group, suggesting that these groups are attracted to the surface. This was further supported by the experiments showing that the PC groups were situated deeper within the film. 相似文献
785.
The potential of ion mobility (IM) spectrometry in combination with mass spectrometry (MS) for real-time reaction monitoring is reported. The combined IM-MS approach using electrospray ionization affords gas-phase analyte characterization based on both mass-to-charge (m/z) ratio and gas-phase ion mobility (drift time). The use of IM-MS analysis is demonstrated for the monitoring of the reaction products formed when 7-fluoro-6-hydroxy-2-methylindole is deprotonated by aqueous sodium hydroxide. Real-time reaction monitoring was carried out over a period of several hours, with the reaction mixture sampled and analysed at intervals of several minutes. Product ion relative intensity is enhanced selectively in the ion mobility-selected mass spectrum, compared to mass spectrometry alone. The combined IM-MS approach has potential as a rapid and selective technique to aid pharmaceutical process control and for the elucidation of reaction mechanism. 相似文献
786.
Sharon Gustard Jalal Fadili Emma J. Williams Laurance D. Hall T. Adrian Carpenter Matthew Brett Edward T. Bullmore 《Magnetic resonance imaging》2001,19(10):389-1331
The effect of slice orientation on reproducibility and sensitivity of 3T fMRI activation using a motor task has been investigated in six normal volunteers. Four slice orientations were used; axial, oblique axial, coronal and sagittal. We applied analysis of variance (ANOVA) to suprathreshold voxel statistics to quantify variability in activation between orientations and between subjects. We also assessed signal detection accuracy in voxels across the whole brain by using a finite mixture model to fit receiver operating characteristic (ROC) curves to the data. Preliminary findings suggest that suprathreshold cluster characteristics demonstrate high motor reproducibility across subjects and orientations, although a significant difference between slice orientations in number of activated voxels was demonstrated in left motor cortex but not cerebellum. Subtle inter-orientation differences are highlighted in the ROC analyses, which are not obvious by ANOVA; the oblique axial slice orientation offers the highest signal detection accuracy, whereas coronal slices give the lowest. 相似文献
787.
Zoltán Sebestyén Ferenc Lezsovits Emma Jakab Gábor Várhegyi 《Journal of Thermal Analysis and Calorimetry》2012,110(3):1501-1509
The thermal behaviours of a sewage sludge sample, woody (black locust, poplar and willow) and herbaceous (energy grass and wheat straw) biomass as well as mixed (sewage sludge and black locust in ratios 1:1 and 1:3) samples were compared under inert and oxidative atmosphere. The thermogravimetric experiments of each sample demonstrate that the beginning temperature of decomposition is similar in inert and oxidative atmospheres, i.e. the primary bond scissions are not affected by the atmosphere. Nevertheless, oxygen increases the decomposition rate and the volatile evolution of all samples at higher temperatures. Thermogravimetry/mass spectrometry (TG/MS) experiments have been performed to determine the mass loss of the samples and the formation of volatile products as a function of temperature in inert atmosphere. Wood and herbaceous biomass samples evolved various organic products (aldehydes, ketones, acids, furan derivatives, etc.) beside water and gaseous products. Sewage sludge released mainly water, carbon oxides, methane, hydrogen, hydrocarbons, ketones, acids as well as sulphur- and nitrogen-containing products. High heating value and low heating value of the samples have been determined by a bomb calorimeter. Principal component analysis (PCA) has been used to find statistical correlation between the data. The results unambiguously support the correlation between the thermogravimetric parameters (e.g. DTGmax) and the heating values of the samples. 相似文献
788.
789.
790.
Brunilde Castano Tommaso Pedrazzini Massimo Sisti Emma Gallo Fabio Ragaini Nicola Casati Alessandro Caselli 《应用有机金属化学》2011,25(11):824-829
The synthesis and characterization of copper(I) complexes of the novel pyridine‐containing macrocyclic ligand (PC‐L) and their use as catalysts in the Henry reaction are reported. The pyridine‐based 12‐membered tetraaza macrocyclic (PC‐L) ligand 1 can be obtained in good overall yield (85%) from commercially available starting materials. The Cu(I) complexes showed good catalytic activities in the Henry reaction of different aldehydes and nitroalkanes. Remarkable diastereoselectivity was observed when isatine was reacted with nitroethane under catalytic conditions. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献