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101.
Ulrich Schllkopf 《Angewandte Chemie (International ed. in English)》1977,16(6):339-348
Being both nucleophilic and electrophilic, α-metalated isocyanides can add to polar double bonds, forming heterocycles. They are also synthons for α-metalated primary amines. This article describes recent or improved procedures for their use in organic synthesis: (1) In heterocyclic syntheses to give 2-oxazolines, 2-imidazolines, 2-thiazolines, oxazoles and oligooxazoles, thiazoles, triazoles, imidazolinones, pyrroles, 5,6-dihydro-1,3-oxazines and -thiazines, and (via cycloaddition with nitrones) 2-imidazolidinones. (2) In the field of formylaminomethylenation, for example transformation of estrone methyl ether and a keto sugar into the corresponding α-formylaminoacrylic esters, and the conversion of aldehydes and ketones by 3- and 4-pyridyl-methyl isocyanides into N-(1-pyridyl-1-alkenyl)formamides and their hydrolysis to 3- and 4-acylpyridines. (3) In connection with the use of α-metalated isocyanides as synthons for α-metalated primary amines, the author demonstrates how they may be used for preparation of 1,2- and 1,3-amino alcohols, 1,2-diamines, 2,3-diaminoalkanoic acids and for synthesis of higher amino acids starting from simple amino acids. 相似文献
102.
1-Aryl-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinolines were prepared according to a one-pot procedure involving the reaction of 2-(3,4-dimethoxyphenyl)-ethylamine with aromatic aldehydes in TFA at reflux. The tetrahydroisoquinolines were treated with H2O2-WO42− in methanol at room temperature to give the corresponding 3,4-dihydroisoquinoline-2-oxides. Treatment of these cyclic nitrones with DMAD in toluene at room temperature gave the corresponding isoxazolo[3,2-a]isoquinolines. These compounds were heated in toluene at reflux to give the corresponding ylides in high yields (Method A). The effect of the substituents on the rate of the rearrangement of such compounds prompted us to discuss a new mechanism involving consecutive C-C bond heterolysis and 1,3-sigmatropic shift. A one-pot reaction involving the treatment of the nitrones with equimolar amounts of DMAD in refluxing toluene also gave the ylides (Method B). The structures of the prepared compounds were elucidated by spectral means and elemental analyses. 相似文献
103.
The complexation equilibria between Ni(II) and Zn(II) metal ions with 3-(1-naphthyl)-2-mercaptopropenoic acid (H2NMP) were studied by glass electrode potentiometry, at 25 °C and 1.0 mol·dm–3 in NaClO4 as constant ionic medium in 50% (v/v) water-ethanol solutions. Formation constants for the complexes Ni(NMP), Ni(NMP)
2
2–
, Zn(NMP) and Zn(NMP)
2
2–
, refined by the MINIGLASS program, are reported. 相似文献
104.
《Indagationes Mathematicae》2022,33(3):598-624
We construct left invariant special Kähler structures on the cotangent bundle of a flat pseudo-Riemannian Lie group. We introduce the twisted cartesian product of two special Kähler Lie algebras according to two linear representations by infinitesimal Kähler transformations. We also exhibit a double extension process of a special Kähler Lie algebra which allows us to get all simply connected special Kähler Lie groups with bi-invariant symplectic connections. All Lie groups constructed by performing this double extension process can be identified with a subgroup of symplectic (or Kähler) affine transformations of its Lie algebra containing a nontrivial 1-parameter subgroup formed by central translations. We show a characterization of left invariant flat special Kähler structures using étale Kähler affine representations, exhibit some immediate consequences of the constructions mentioned above, and give several non-trivial examples. 相似文献
105.
Photoproducts of pyridoxal-5-P, i.e., 4-pyridoxic-5-P and bis-pyridoxal-5-P, have been studied by spectroscopic methods. The spectroscopic properties of bis-pyridoxal-5-P (bis-PLP) resemble those of pyridoxal-5-P (PLP) under similar experimental conditions. The coupling of methylen hydrogens to the phosphorus atom has been shown by NMR spectroscopy. The singlet in the31P-NMR spectra and the triplet in1H-undecoupled experiments confirm the presence of the phosphate group in the 5 position of the structure of the vitamin. The effect of pH and solvent composition on the relative distribution of species of bis-pyridoxine-5-P (bis-PNP) has been investigated by absorption and fluorescence spectroscopy. The acid-base dissociation of the phosphate group is easily detected by emission spectroscopy. Bis-PNP and bis-PLP bind to the enzyme RNase A and they behave as competitive inhibitors with respect to the substrate cytidine-2-3-cyclic phosphate. The natural forms of vitamin B6, pyridoxine, and pyridoxine-5-P have no effect on the catalytic activity of the protein. Experimental evidence derived from fluorescence and inhibition experiments is consistent with the hypothesis that bis-PNP recognizes the catalytic site of RNase A. 相似文献
106.
LIZHIBIN SHIHE 《高校应用数学学报(英文版)》1996,11(1):1-6
Abstract. We consider the following simplified model for the Belousou-Zhabotinskii(B-Z)reaction: 相似文献
107.
J. Ignacio Extremiana Aldana L. Javier Herná ndez Paricio M. Teresa Rivas Rodrí guez 《Proceedings of the American Mathematical Society》1996,124(11):3545-3553
For each integer , we give a distinct closed model category structure to the category of pointed spaces such that the corresponding localized category is equivalent to the standard homotopy category of -connected CW-complexes. The structure of closed model category given by Quillen to is based on maps which induce isomorphisms on all homotopy group functors and for any choice of base point. For each , the closed model category structure given here takes as weak equivalences those maps that for the given base point induce isomorphisms on for .
108.
Y. Zhang 《Journal of Optimization Theory and Applications》1993,77(2):323-341
This paper concerns solving an overdetermined linear systemA
T
x=b in the leastl
1-norm orl
-norm sense, whereA
m×n
,m<n. We show that the primal-dual interior point approach for linear programming can be applied, in an effective manner, to linear programming versions of thel
1 andl
-problems. The resulting algorithms are simple to implement and can attain quadratic or superlinear convergence rate. At each iteration, the algorithms must solve a linear system with anm×m positive-definite coefficient matrix of the formADA
T
, whereD is a positive diagonal matrix. The preliminary numerical results indicate that the proposed algorithms offer considerable promise.This research was supported in part by Grants NSF DMS-91-02761 and DOE DE-FG05-91-ER25100. 相似文献
109.
Heng-Dao Quan Hui-E Yang Masanori Tamura Akira Sekiya 《Journal of fluorine chemistry》2007,128(3):190-195
In this report, a simple process for preparing HFC-245fa through the reaction of 1,1,1,3,3-pentachloropropane (PCP) and anhydrous HF via two-step vapor-phase catalytic fluorination is described. The antimony pentafluoride catalyst was supported on inert porous materials to improve the catalytic activity. The resulting process catalyst not only exhibited high catalytic activity and excellent thermo-stability, but also improved the performance of SbF5, in terms of hygroscopicity and corrosion. 相似文献
110.
Molybdenum was reported to be precipitated quantitatively by 8-hydroxyquinoline in the pH range 3.3–7.6, the precipitated compound having the composition MoO2(ox)2. The pH range reported and the composition of the complex do not seem to be compatible with present knowledge of the pH stability of anionic and cationic molybdenum. It is now shown that under defined conditions, the precipitate is not formed at pH values higher than 2.24. In several estimations of other metals, molybdenum was masked by using a complexone at high pH values. It is now pointed out, that maintaining the solution at high pH value is itself sufficient and no other external complexing agent is necessary for masking molybdenum. 相似文献