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901.
902.
刘铸晋等在测定钩吻素子1结构的工作中,发现1能被钠-醇还原裂解,亚胺基β位的醚键发生断裂,得到还原裂解产物——双氢钩吻醇2~([1])。其反应机理可能是一种自由基-阴离子反应,类似于苄基醚的还原断裂。如图式1所示: 反应的关键一步是一个单电子在化合物1中的碳氮双键上的加成,生成一个自由基-阴离子,接着发生β键的断裂及质子化。这种过程连续进行三次以后,就能获得还原裂解产物2。很明显,反应的决速一步是自由基的生成~([2])。为了进一步探讨这一反应的应用范围,我们合成了一系列具有各种亚胺体系的模型化合物,研究他们在钠-醇溶液中的反应情况。这些模型化合物是一系列的Schiff碱(见表1)。 相似文献
903.
A simple reversed-phase high-performance liquid chromatographic method employing C-18 column has been developed for simultaneous analysis of three intermediates in the synthesis of S-duloxetine, the antidepressant drug, viz., 2-acetyl thiophene (AT), N,N-dimethyl-3-keto-(2-thienyl)-propanamine (DKTP) and (S)-N,N-dimethyl-3-hydroxy-(2-thienyl)-propanamine (DHTP). Good separations were achieved by employing an isocratic system using acetonitrile and 0.05 M phosphate buffer (pH 7.0) containing 0.02% diethylamine. The detection was carried out at 241 nm. The method was validated for linearity, range, accuracy and precision. The developed method was applied for monitoring the progress of chemical synthesis of DKTP from AT followed by the biocatalytic reduction of DKTP to DHTP as the disappearance of the substrate and formation of the product can be monitored simultaneously by the present method. 相似文献
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Anita T.?LaytonEmail author Michael L.?MinionEmail author 《BIT Numerical Mathematics》2005,45(2):341-373
This paper concerns a class of deferred correction methods recently developed for initial value ordinary differential equations;
such methods are based on a Picard integral form of the correction equation. These methods divide a given timestep [tn,tn+1] into substeps, and use function values computed at these substeps to approximate the Picard integral by means of a numerical
quadrature. The main purpose of this paper is to present a detailed analysis of the implications of the location of quadrature
nodes on the accuracy and stability of the overall method. Comparisons between Gauss-Legendre, Gauss-Lobatto, Gauss-Radau,
and uniformly spaced points are presented. Also, for a given set of quadrature nodes, quadrature rules may be formulated that
include or exclude function values computed at the left-hand endpoint tn. Quadrature rules that do not depend on the left-hand endpoint (which are referred to as right-hand quadrature rules) are
shown to lead to L(α)-stable implicit methods with α≈π/2. The semi-implicit analog of this property is also discussed. Numerical results suggest
that the use of uniform quadrature nodes, as opposed to nodes based on Gaussian quadratures, does not significantly affect
the stability or accuracy of these methods for orders less than ten. In contrast, a study of the reduction of order for stiff
equations shows that when uniform quadrature nodes are used in conjunction with a right-hand quadrature rule, the form and
extent of order-reduction changes considerably. Specifically, a reduction of order to
is observed for uniform nodes as opposed to
for non-uniform nodes, where Δt denotes the time step and ε a stiffness parameter such that ε→0 corresponds to the problem becoming increasingly stiff.
AMS subject classification (2000) 65B05 相似文献
909.
In this note new Rosenbrock methods for ODEs, DAEs, PDEs and PDAEs of index 1 are presented. These solvers are of order 3,
have 3 or 4 internal stages, and fulfil certain order conditions to obtain a better convergence if inexact Jacobians and approximations
of
are used. A comparison with other Rosenbrock solvers shows the advantages of the new methods.
AMS subject classification (2000) 34A09, 65L80 相似文献
910.
Theoretical expressions for the covalence reduction factors of orbital angular momentum and spin-orbit coupling in pseudo-tetrahedral four-coordinated paramagnetic complexes withD 2d symmetry, denoted ask's andR's respectively, have been derived. p ]The mixing coefficients in the antibonding MO's for the CuCl 4 2- ion in three complexes are estimated using suitable approximations. It is shown thatk's must be less thanR's in Tinkham's approximation. Certain misconceptions existing in the literature regarding the value of the integral 〈p u |???u|s〉 have been clarified. 相似文献