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471.
The preparation of 3,3-difluoro-6-methylhept-5-en-2-one 1, a key intermediate for the synthesis of 4,4-difluoroterpenes, and applications in linalool and geraniol series are described. The process involves 1,1-difluoro-2-trimethylsilyoxypropene, an enol silyl ether prepared from acetyltrimethylsilane and trifluoromethyltrimethylsilane, and its reaction in situ with prenyl benzoate, under catalysis by trimethylsilyl trifluoromethanesulfonate. Optimized conditions leading to either the desired enol silyl ether or the unprecedented methyl(trifluoromethyl)trimethylsilyl carbinol 4 have been achieved. The prenylation of the enol silyl ether gives a 9/1 mixture of regioisomers, in favor of the expected ketone 1. Treatment of 1 with vinylmagnesium bromide leads to (+/-)-4,4-difluorolinalool 7. Reaction with the lithium enolate of ethyl diethylphosphonoacetate, and then LAH reduction, converts 1 to 4,4-difluorogeraniol 11, with complete stereoselectivity. 相似文献
472.
Electronic band systems of the gaseous diatomic compounds of copper and various X elements of the 14th column (Si, Ge, Sn, Pb) have been observed by thermal excitation in the red part of the visible spectrum. Vibrational analysis of the two subsystems observed for each of these molecules (except for CuPb with only one system) are reported and assigned as (2)Sigma(+)-(2)Pi(3/2) and (2)Sigma(+)-(2)Pi(1/2) transitions. The variation of the spin-orbit splitting of the (2)Pi lower states from CuSi to CuSn follows closely that of the np shell spin-orbit parameters in the group 14 atoms. This fully corroborates previous ab initio calculations that predict a (2)Pi(r) ground state with the ionic Cu(+) (3d(10))X(-)(pvarsigma(2)ppi) configuration for these molecules. Copyright 2000 Academic Press. 相似文献
473.
474.
锂离子储能器件具有高能量密度与绿色环保等优点, 在未来新能源汽车和大规模储能领域中将显示出巨大的潜力. 然而, 由于传统锂离子负极材料如石墨、 硅存在电化学动力学缓慢与高倍率下的安全性等问题, 无法满足目前能源消费终端日益增长的快速充放电性能要求. 因此, 开发有利于锂离子快速嵌入/脱出、 安全性与稳定性优异的负极材料至关重要. 相比于传统的负极材料, 铌基氧化物具有合适的理论容量、 更安全的工作电位、 稳定且快速的离子传输通道等优点. 本文综述了高倍率铌基氧化物负极材料在锂离子储能器件领域的最新研究进展, 重点介绍了典型铌基氧化物的储锂机理与改性手段, 并对铌基氧化物负极材料未来的发展与挑战进行了展望. 相似文献
475.
Rozanska X Sautet P Delbecq F Lefebvre F Borshch S Chermette H Basset JM Grinenval E 《Physical chemistry chemical physics : PCCP》2011,13(35):15955-15959
The process of grafting H(3)PMo(12)O(40) onto silica surfaces is studied using periodic density functional theory methods. For surfaces with a high hydroxyl coverage, the hydroxyl groups are consumed by the polyoxometalate protons, resulting in water formation and the creation of a covalent bond between the polyoxometalate and the surface, and mostly no remaining acidic proton on the polyoxometalate. When the surfaces are partially dehydroxylated and more hydrophobic, after temperature pretreatment, less covalent and hydrogen bonds are formed and the polyoxometalate tends to retain surface hydroxyl groups, while at least one acidic proton remains. Hence the hydroxylation of the surface has a great impact on the chemical properties of the grafted polyoxometalate. In return, the polyoxometalate species affects the compared stability of the partially hydroxylated silica surfaces in comparison with the bare silica case. 相似文献
476.
Zhang S Féret A Lefebvre H Tessier M Fradet A 《Chemical communications (Cambridge, England)》2011,47(39):11092-11094
The polyetherification of diols with 4-12 methylene units was studied in Br?nsted Acid Ionic Liquids (BAILs). High molar mass poly(oxyalkylene)s were obtained at relatively low temperatures (130 °C), except in the cases of 1,4-butanediol and 1,6-hexanediol where cyclic ether formation was observed. 相似文献
477.
Dimitri Lefebvre 《Nonlinear Analysis: Hybrid Systems》2011,5(3):394-406
Reliability analysis is often based on stochastic discrete event models like stochastic Petri nets (SPNs). For large dynamical systems with numerous components, the analytical expression of the SPNs steady state is full of complexities because of the combinatory explosion with discrete models. Moreover, the estimation of mean markings thanks to simulations is time consuming in case of rare events. For these reasons, Petri net fluidification may be an interesting alternative to provide a reasonable estimate of the asymptotic behavior of stochastic processes. Unfortunately, the steady states of SPNs and timed continuous Petri nets (contPNs) with the same structure, same initial marking and same firing rates are mainly often different. The region of SPN steady states (when firing rates are defined in a polyhedral area) contrasts with that of contPN ones. The purpose of this paper is to illuminate this issue in taking advantage of the piecewise-affine hybrid structure of contPNs. Regions and critical regions are defined in the marking space in order to characterize this structure. Based on this characterization, the main contribution is to propose a transformation of the considered SPN into a contPN with the same structure, modified firing rates and homothetic initial marking so that the corrected contPN converges partially to the same mean marking than the SPN. Consequently, a global understanding of an SPN steady state can be obtained according to the corrected contPN. 相似文献
478.
Marie-Christine Pauzin Bruno Cochelin Jean-Pierre Lefebvre 《Journal of sound and vibration》2011,330(5):987-1004
The radial responses of free and encapsulated microbubbles excited by an ultrasonic plane wave with a large wavelength in comparison with the bubble size are governed by NonLinear Ordinary Differential Equations (NL-ODEs). The nonlinear frequency response gives the harmonic content of the time response and constitutes the expected outcome of a high order harmonic analysis. In this paper, high order harmonic balance analysis of modified “RPNNP” (bubble), Hoff and Marmottant (contrast agents) models is performed with an open-source software program. For this purpose, the original NL-ODEs are recast into nonlinear systems in which the nonlinearities are at most quadratic. In the spectral domain, this recast provides close form and aliasing-free solutions of arbitrarily large numbers of harmonics. Relevant quantities such as primary and secondary resonances and the nonlinear amplitude threshold of the excitation wave are evaluated. The frequency curves drawn up characterize the bending and quantify the jump frequencies and amplitudes of each harmonic component. The results obtained with this predictive method confirm that it should provide a useful tool for nonlinear bubble detection and sizing and for contrast agent designing. 相似文献
479.
本文利用生成函数方法对存在初始分布的自缩合乙烯基聚合反应体系进行研究.首先在任意初始分布情形下,构造并通过反应体系的微分动力学方程导出对应的生成函数.进一步分别考察了均一初始分布和混合初始分布两种情形,利用生成函数获得反应体系的数均、重均和Z-均聚合度以及多分散指数等物理量.研究结果表明,利用生成函数方法不仅可以给出超支化高分子的数量分布函数,而且可以使平均高分子物理量的计算大为简化.同时发现,反应体系的统计特征与初始分布密切相关,相应的结果可为进一步研究分批投料、多组分及非等活性等更加复杂的自缩合乙烯基反应体系提供可能的基础. 相似文献
480.
微波消解-电感耦合等离子质谱法同时测定烟用香精中24种微量元素 总被引:1,自引:0,他引:1
采用微波消解处理样品,电感耦合等离子体质谱检测的方法同时测定了8种烟用香精样品中的24种微量元素。方法以锗和钍作为内标消除基体效应,采用灌木枝叶标准物质(GBW07602)对方法进行验证。结果表明:24种微量元素的检测限在0.004~1.078ng/mL之间;相对标准偏差均小于10%;回收率在84.46%~108.85%之间。该法操作简单、分析快速、灵敏度高、准确度好,适合批量香精样品中微量元素的检测。 相似文献