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排序方式: 共有72条查询结果,搜索用时 11 毫秒
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Garcia Ruano JL Alcudia A del Prado M Barros D Maestro MC Fernandez I 《The Journal of organic chemistry》2000,65(10):2856-2862
The addition of the lithium anions derived from (R)- and (S)-methyl and -ethyl p-tolyl sulfoxides to (S)-N-benzylidene-p-toluenesulfinamide provides an easy access route to enantiomerically pure beta-(N-sulfinyl)amino sulfoxides. Stereoselectivity can be achieved when the configurations at the sulfur atoms of the two reagents are opposite (matched pair), thus resulting in only one diastereoisomer, even for the case in which two new chiral centers are created. The N-sulfinyl group primarily controls the configuration of the carbon bonded to the nitrogen, whereas the configuration of the alpha-sulfinyl carbanion seems to be responsible for the level of asymmetric induction, as well as for the configuration of the new stereogenic C-SO carbon in the reactions with ethyl p-tolyl sulfoxides. An efficient method for transforming the obtained beta-(N-sulfinyl)amino sulfoxides into optically pure beta-amino alcohols, based on the stereoselective non-oxidative Pummerer reaction, is also reported. 相似文献
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Garcia Ruano JL Alemparte C Martin Castro AM Adams H Rodriguez Ramos JH 《The Journal of organic chemistry》2000,65(23):7938-7943
The behavior of (Z)-3-p-tolylsulfinylacrylonitrile (1) as a chiral dienophile has been evaluated from its reactions with furan and acyclic dienes. Electrostatic interactions of the cyano group with the sulfinyl one restrict the conformational mobility around the C-S bond, thus controlling the pi-facial selectivity, which is almost complete in all cases, the approach of the diene from the less-hindered face of the dienophile (that bearing the lone electron pair) in the predominant rotamer being the favored one. The regioselectivity is also completely controlled by the cyano group. Additionally, the reactivity of compound 1 as well as its endo-selectivity are both higher than those observed for the corresponding (Z)-3-sulfinylacrylates, thus proving the potential of sulfinylnitriles as chiral dienophiles. 相似文献
5.
The space group of alpha(')-NaV2O5 turns below T(c) = 34 K from Pmmn with all V sites equivalent, into Fmm2 with three independent vanadium sites per layer. This is incompatible with models of charge ordering into V4+ and V5+. Our structure determination indicates that the phase transition consists of a charge ordering with three distinct valence states, formally V4+, V4.5+, and V5+. The singlet formation is not associated with dimerization on the spin ladder, but with the formation of spin clusters. Finally, we ascribe the quadrupling of the c axis to the large polarizability of the V2O5 skeleton. 相似文献
6.
Acoustic performance in ultrasonic transmitters can be improved by means of a suitable electrical driving response and matching/tuning networks. It is important to predict this electrical response, but doing so is not easy because it departs notably from the nominal pattern with the loading probes. In practice, the analysis of HV pulser spikes in NDE applications requires fairly complex models in the transient regime and, in addition, non-linear problems could arise, especially in the case of tuned transmitters. In this paper, the most relevant influences of loading characteristics of NDT ultrasonic probes on the pulser electrical driving responses are evaluated in time and frequency domains. Conventional pulse generators and typical NDE pulsers are considered. Driving responses are analysed across commercial ultrasonic probes and, alternatively, across similar purely electrical loads. Distinct influences on pulser responses from electrical and motional sections of the probes are identified. All these aspects are studied on the basis of experimental and computer results. 相似文献
7.
This paper presents a new method for scaling up multiphase flow properties which properly accounts for boundary conditions on the upscaled cell. The scale-up proposed does not require the simulation of a complete finely-gridded model, instead it calls for assumptions allowing the calculation of the boundary conditions related to each block being scaled up. To upscale a coarse block, we have to assume or determine the proper boundary conditions for that coarse block. To date, most scale-up methods have been based on the assumption of steady-state flow associated with uniform fractional flows over all the boundaries of the coarse block. However, such an assumption is not strictly valid when we consider heterogeneities. The concept of injection tubes is introduced: these are hypothetical streamtubes connecting the injection wellbore to all inlet faces of the fine grid cells constituting the block to be scaled up. Injection tubes allow the capturing of the fine-scale flow behavior of a finely-gridded model at the inlet face of the coarse block without having to simulate that fine grid. We describe how to scale up an entire finely-gridded model sequentially using injection tubes to determine the boundary conditions for two-phase flow. This new scale-up method is able to capture almost exactly the fine-scale two-phase flow behavior, such as saturation distributions, inside each isolated coarse-grid domain. Further, the resultant scaled-up relative permeabilities reproduce accurately the spatially-averaged performance of the finely-gridded model throughout the simulation period. The method has been shown to be applicable not only to viscous-dominated flow but also to flow affected by gravity for reasonable viscous-to-gravity ratios. 相似文献
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This paper concerns the switching on of two-dimensional time-harmonic scalar waves. We first review the switch-on problem for a point source in free space, then proceed to analyse the analogous problem for the diffraction of a plane wave by a half-line (the ‘Sommerfeld problem’), determining in both cases the conditions under which the field is well-approximated by the solution of the corresponding frequency domain problem. In both cases the rate of convergence to the frequency domain solution is found to be dependent on the strength of the singularity on the leading wavefront. In the case of plane wave diffraction at grazing incidence the frequency domain solution is immediately attained along the shadow boundary after the arrival of the leading wavefront. The case of non-grazing incidence is also considered. 相似文献
9.
G. B. Scott D. E. Lacklison J. L. Page J. Hewett 《Applied Physics A: Materials Science & Processing》1976,9(1):71-77
The absorption (α) and Faraday rotation (θ) spectra of 14 garnets belonging to the series Bi
x
Sm3-x
Fe5-y
Ga
y
O12 (0<x<1.05, 0.8<y<1.15) have been measured between 15 000 cm−1 and 19 000 cm−1. The figure of merit (θ/α) at 17 850 cm−1 (560 nm) increases linearly with increasing bismuth concentration up tox∼0.6 where it begins to increase less rapidly. For operation of magneto-optic display devices at 17 850 cm−1 there is no advantage in using garnets in this series withx>0.8. The Faraday rotation at 17 850 cm−1 increases linearly with bismuth concentration whereas the absorption coefficient increases more rapidly. The presence of
Bi3+ increases the intensity of all Fe3+ pair transitions in the garnet system as a result of the increased superexchange induced by Bi3+. This is in keeping with the observation that the intensity of the6A1g
(S)→4T1g
(G) transition in (RE)3Fe5O12 (RE=Er, Y, Dy, Gd, Eu) increases on traversing the above RE series as do the Curie temperatures of these iron garnets. 相似文献
10.