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The asymmetric syntheses of the C-1 sidechains of zaragozic acid A and C are described. Aldol reaction defines the chirality at C-4′and C-5′in two independent routes. Multigram preparation as well as a route amenable to derivatization are highlights of these approaches. 相似文献
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A general and convenient synthesis of N-aryl piperazines from bis(2-chloroethyl)amine hydrochloride and a broad range of anilines in diethylene glycol monomethyl ether is described. 相似文献
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Jarvis MW Daily JW Carstensen HH Dean AM Sharma S Dayton DC Robichaud DJ Nimlos MR 《The journal of physical chemistry. A》2011,115(4):428-438
The pyrolysis of 2-phenethyl phenyl ether (PPE, C(6)H(5)C(2)H(4)OC(6)H(5)) in a hyperthermal nozzle (300-1350 °C) was studied to determine the importance of concerted and homolytic unimolecular decomposition pathways. Short residence times (<100 μs) and low concentrations in this reactor allowed the direct detection of the initial reaction products from thermolysis. Reactants, radicals, and most products were detected with photoionization (10.5 eV) time-of-flight mass spectrometry (PIMS). Detection of phenoxy radical, cyclopentadienyl radical, benzyl radical, and benzene suggest the formation of product by the homolytic scission of the C(6)H(5)C(2)H(4)-OC(6)H(5) and C(6)H(5)CH(2)-CH(2)OC(6)H(5) bonds. The detection of phenol and styrene suggests decomposition by a concerted reaction mechanism. Phenyl ethyl ether (PEE, C(6)H(5)OC(2)H(5)) pyrolysis was also studied using PIMS and using cryogenic matrix-isolated infrared spectroscopy (matrix-IR). The results for PEE also indicate the presence of both homolytic bond breaking and concerted decomposition reactions. Quantum mechanical calculations using CBS-QB3 were conducted, and the results were used with transition state theory (TST) to estimate the rate constants for the different reaction pathways. The results are consistent with the experimental measurements and suggest that the concerted retro-ene and Maccoll reactions are dominant at low temperatures (below 1000 °C), whereas the contribution of the C(6)H(5)C(2)H(4)-OC(6)H(5) homolytic bond scission reaction increases at higher temperatures (above 1000 °C). 相似文献
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David J. Robichaud Daniel Lisak Charles E. Miller 《Journal of Quantitative Spectroscopy & Radiative Transfer》2008,109(3):435-444
We describe a high-precision method for measuring pressure shifting of absorption lines. The technique involves the acquisition of high-resolution spectra using a cavity ring-down spectrometer whose length is continuously locked to a frequency-stabilized reference laser over a range of sample pressures. We discuss a relatively large correction arising from the pressure-dependence of dispersion in the cavity modes, and we demonstrate pressure shifting measurements in air for transitions in the 16O2A-band. Pressure shifts in the range -0.011 to are reported. We measured relative positions of line centers to within 70 kHz and determined pressure shifting coefficients over a 5 kPa pressure range with relative uncertainties approximately equal to 1.0%, which constitutes a five-fold improvement over previous measurements. 相似文献
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Balaji Subramanian Nadjda Tchoukanova Yahia Djaoued Claude Pelletier Mathieu Ferron Jacques Robichaud 《Journal of Raman spectroscopy : JRS》2014,45(4):299-304
Recent research interests in geometrical isomers of astaxanthin (AST) are motivated by their metabolic activities in aquatic animals and human. It has been established that cis‐isomers of AST are selectively absorbed in human plasma during the metabolic process; however, exact absorption mechanism is still unclear. Hence, a detailed investigation of the structural and optical properties of geometrical isomers of AST is required. Among the techniques available for the study of AST and other carotenoids, Raman spectroscopy has been much acclaimed. Raman spectra have been shown to be influenced by the electronic and mechanical confinement effects arising from the conjugated polyene chain of carotenoids. In this work, we present Raman studies of geometrical isomers of AST, along with their optical absorption characteristics. Geometrical isomers of AST were prepared by heating all trans‐AST in solution form, and the isomers were separated using high performance liquid chromatography. Optical absorption spectra of cis‐isomers of AST showed hypsochromic shifts in the main absorption band and formation of new bands at lower wavelengths. A detailed Raman spectral analysis performed on the cis‐isomers of AST showed new modes which have not been observed and accounted for so far. In addition, we demonstrate that the electronic and mechanical confinement effects in the polyene chain of AST play an important role in the Raman spectra of geometrical isomers of AST. It is anticipated that this work will demonstrate that Raman spectroscopy is an important diagnostic tool in distinguishing and identifying the geometrical isomers of AST. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
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[reaction: see text] The first synthesis of (-)-panacene has been accomplished in concise, highly stereoselective fashion from commercially available 2-methoxy-6-methylbenzoic acid (15 steps, 8.3% overall yield). The synthesis unambiguously establishes the correct relative and absolute configuration of panacene, and demonstrates the serviceability of Pd(II)-mediated tandem intramolecular alkoxycarbonylation-lactonization for the expedient assembly of its tricyclic core, and the dual role of asymmetric alkynylation as an initial source of chirality and as a powerful tool for manipulating diastereoselectivity. 相似文献
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A general and convenient one-pot synthesis of highly substituted indolines from arylhydrazines and aldehydes is reported. This synthesis allows introduction of substitution at essentially all positions of the indoline nucleus to achieve significant diversity in this biologically important template. 相似文献
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Djaoued Y. Badilescu S. Ashrit P.V. Bersani D. Lottici P.P. Robichaud J. 《Journal of Sol-Gel Science and Technology》2002,24(3):255-264
Nanocrystalline titania films were prepared by a complexing agent-assisted sol-gel dip-coating process. The effect of acetylacetone, diethanolamine and polyethylene glycol on the structure of the heat-treated titania films was examined by Raman and FTIR spectroscopy and X-ray diffraction. The effect the complexing agents have on the anatase to rutile phase transition during the heat treatment process is studied. The understanding of this effect is expected to enhance our capacity to tailor the composition and morphology of films and thus their properties. The Raman and the infrared spectra of nanocrystalline titania films and the changes induced by the heat treatment were also investigated. We have also studied the size of the crystallites in TiO2 films and its dependence on the type of complexing agent used. 相似文献