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41.
The ring expansion of prolinols via an aziridinium intermediate gives C3‐substituted piperidines in good yields and enantiomeric excess, the substituent at the C3 position being derived from the most reactive nucleophile in the reaction mixture. Depending on the nucleophile, the reaction proceeds under thermodynamic or kinetic control. The regioselectivity of attack of nucleophiles on the aziridinium intermediate depends on the nature of the substituents on the nitrogen atom and the C4 position of the starting prolinols.  相似文献   
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The synthesis, characteristics, properties, and reactions with metallic ions of pycolinaldehyde derivatives of Girard-P reagent have been studied. The reagents form complexes with Cu(II), Ni(II), Co(II), Hg(II) and (I), Zn(II), Cd(II), and Fe(III), and (II), which exhibit a good sensibility but whose spectra have the absorption maxima located in the ultraviolet zone. The spectrum of copper complex in the presence of ascorbic acid shows another absorption band at the visible region and this makes the spectrophotometric determination of copper very selective. The influence of the different experimental parameters on the formation of copper complex without ascorbic acid and with this compound was studied, and the optimum conditions for the determination of copper were established. The precision of the procedure, expressed in terms of relative standard deviation, was 1.1%. The method has been tested on “white metal E-8” samples.  相似文献   
45.
We report a virtual Compton scattering study of the proton at low c.m. energies. We have determined the structure functions P(LL)-P(TT)/epsilon and P(LT), and the electric and magnetic generalized polarizabilities (GPs) alpha(E)(Q2) and beta(M)(Q2) at momentum transfer Q(2)=0.92 and 1.76 GeV2. The electric GP shows a strong falloff with Q2, and its global behavior does not follow a simple dipole form. The magnetic GP shows a rise and then a falloff; this can be interpreted as the dominance of a long-distance diamagnetic pion cloud at low Q2, compensated at higher Q2 by a paramagnetic contribution from piN intermediate states.  相似文献   
46.
We have measured the transverse asymmetry A(T') in 3He(e,e(')) quasielastic scattering in Hall A at Jefferson Laboratory with high precision for Q2 values from 0.1 to 0.6 (GeV/c)(2). The neutron magnetic form factor G(n)(M) was extracted based on Faddeev calculations for Q2 = 0.1 and 0.2 (GeV/c)(2) with an experimental uncertainty of less than 2%.  相似文献   
47.
Generic computer simulations using empiric interatomic potentials suggest a new, collective mechanism that could be responsible for mixing at heteroepitaxial interfaces. Even if single adsorbate atoms diffuse by hopping on the substrate surface and do not mix at the terraces, two-dimensional islands formed by nucleation may become unstable above a certain critical size and explode upwards forming clusters of several atomic layers. This process is accompanied by strong distortions of the underlying atomic layers, and on soft materials it can result in surface etching and incorporation of substrate atoms into the islands.  相似文献   
48.
We report an experimental confirmation of the power-law relationship between the critical anisotropy parameter and ion number for the linear-to-zigzag phase transition in an ionic crystal. Our experiment uses laser cooled calcium ions confined in a linear radio-frequency trap. Measurements for up to ten ions are in good agreement with theoretical and numeric predictions. Implications on an upper limit to the size of data registers in ion trap quantum computers are discussed.  相似文献   
49.
张发  刘有成 《化学学报》1989,47(11):1120-123
本文采用取样直流极谱, 常规脉冲极谱, 微分脉冲极谱和交流极谱考察了,2,2,6,6-四甲基-4-羟基哌啶 -1-氧和2,2,6,6-四甲基-4-氧哌啶 -1-氧由基及2,2,6,6-四甲基哌啶 -1-氧自由基在水溶液中的还原反应, 并研究了它们的还原经历电化学过程 。  相似文献   
50.
刘有成  张发  江致勤 《化学学报》1987,45(4):477-483
循环伏安法研究表明,2,2,6,6-四甲基-4-羟基哌啶-1-氧自由基和2,2,6,6-四甲基-4-氧哌啶-1-氧自由基,在水溶液中的单电子氧化电极反应的可逆性随介质酸性,扫描速度和自由基浓度增加而增加,表明电极氧化产物可进一步发生化学反应.  相似文献   
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