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1.
Summary Multiflorine (1) — a minor lupine alkaloid — treated by methyl lithium or methyl magnesium iodide affords 4S-4-hydroxy-4-methyl-2,3-didehydrosparteine (2) and 2S-2-methyl-4-oxosparteine (3), respectively, as the dominating products. Their steric structure, determined by1H and13C NMR techniques, points to stereospecific preferences of these reactions. The observed nucleophilic 1,2- and 1,4-additions indicate that regiospecificity of the action of MeLi or MeMgI on multiflorine is different from that of the so far known similar alkylation of other enamino ketones.
Die räumliche Struktur von Methylierungsprodukten des Multiflorins
Zusammenfassung Multiflorin (1), ein Lupin-Nebenalkaloid, ergibt bei Umsetzung mit Methyllithium oder Methylmagnesiumiodid 4S-4-Hydroxy-4-methyl-2,3-didehydrospartein (2) und 2S-2-Methyl-4-oxospartein (3) als Hauptprodukte. Ihre NMR-spektroskopisch (1H und13C) aufgeklärte räumliche Struktur weist auf eine Stereoselektivität der erwähnten Reaktionen hin. Die beobachteten nucleophilen 1,2- und 1,4-Additionen zeigen, daß sich die Regiospezifität der Einwirkung von MeLi oder MeMgl auf Multiflorin von jener bis jetzt bekannter Alkylierungen von Enaminoketonen unterscheidet.相似文献
2.
Let be a product order on [n]
p
i.e. for A, B [n]
p
, 1a
1<a
2<...<a
p
º-n and 1<-b
1<b
2<...<b
p
<-n we have AB iff a
i<-b
i for all i=1, 2,..., p. For a linear extension < of (ordering [n]
p
as
) let F
<
[n],p
(m) count the number of A
i
's, i<-m such that 1A
i. Clearly,
for every m and <, where <l denotes the lexicographic order on [n]
p
. In this note we prove that the colexicographical order, <c, provides a corresponding lower bound i.e. that
holds for any linear extension < of .This project together with [2] was initiated by the first author and continued in colaboration with the second author. After the death of the first author the work was continued and finalized by the second and the third author.Research supported by NSF grant DMS 9011850. 相似文献
3.
4.
5.
An effective algorithm for estimating the reliability of frame structures made of an elastic perfectly plastic material is presented. It is assumed that the structure is working in uniaxial state of stress, the material parameters and the limit values of the loads are described by random variables, all loads are acting in a static manner, the probability density functions of all random variables, which describe the structure and loads are known. As the structure reliability measure the probability of failure and corresponding reliability index are regarded. The dead (constant) load and the climatic loads are taken into account. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
6.
Wagner José Barreto Sonia Regina Giancoli Barreto Waleria Pickina Silva 《Transition Metal Chemistry》2009,34(6):677-681
The reaction between Fe(III) and dopamine in aqueous solution in the presence of Na2S2O3 was followed through UV–Vis spectroscopy, pH and oxy-reduction potential (Eh) measurements. The formation and quick disappearing
of the complex [Fe(III)HL1−]2+, HL1− = monoprotonated dopamine was observed with or without S2O3
2− at pH 3. An unexpected reaction occurs in presence of thiosulfate forming the stable anion complex [Fe(III)(L2−)2]1−, L2− = dopacatecholate (λ = 580 nm) and the auto-increasing of the pH, from 3 to 7. It was proposed that H+ and molecular oxygen are consumed by free radical thiosulfate formed during the reaction. 相似文献
7.
Jacek Thiel Władysław Boczoń Waleria Wysocka 《Monatshefte für Chemie / Chemical Monthly》2000,131(10):1073-1081
Summary. The bisquinolizidine carbinolamine 17-hydroxylupanine was synthesized de novo from lupanine using 2,3-dichloro-5,6-dicyano-1,4-benzoquinone; its structure was established by NMR techniques. The equatorial
position of the hydroxy group as well as the prevailing boat form of ring C were determined. As expected, the carbinolamine
converted into the C17=N16 anhydronium perchlorate upon treatment with HClO4. NMR analysis of the salt revealed a conformational equilibrium within rings A and D, whereas rings B and C remain rigid.
Received March 13, 2000. Accepted March 21, 2000 相似文献
8.
Waleria Janczak T. Milobedzki J. F. Grebski H. Gravestein A. W. F. Middelberg A. Frey-Wyssling und K. Kanamaru 《Fresenius' Journal of Analytical Chemistry》1938,114(1-2):74-80
Ohne Zusammenfassung 相似文献
9.
The examined compounds crystallize in the monoclinic space groupsP2
1/c (phenyl derivative,1) andP2
1/a (benzyl derivative,2). The unit cell parametersa, b, c (Å) and (°) were: 6.402(1), 16.506(1), 10.144(1), 97.48(1) for1 and 12.099(2), 4.612(1), 21.712(4) and 105.20(2) for2. The finalR(Rw) factors were 0.043 (0.041) and 0.121 (0.126) for1 and2, respectively. Both molecules have similar geometry of the bicyclic system with flat 1,2,4-triazole rings, sofa conformations of 1,3-thiazole ones and axial hydroxy groups. In the crystals the molecules form infinite chains (by means of O–H...N(4) hydrogen bonds), enantiomeric in1 and racemic in2. 相似文献
10.
Szymon Dziomba Magdalena Wysocka Joanna Jońca Laura Sola Aleksandra Steć Krzysztof Waleron Bartosz Wielgomas 《Electrophoresis》2021,42(20):2010-2017
The capillary zone electrophoresis (CZE) has recently been proposed by our group as a novel technique for outer membrane vesicles (OMVs) characterization (J. Chromatography 1621 (2020) 461047). In present work the impact of selected parameters of CZE method on OMVs isolates analysis was assessed. It was shown that the extension of sample injection plug length significantly improves the detectability of macromolecular aggregates in CZE. Moreover, a negligible adsorption of OMVs to both uncoated and polymer-modified (poly(DMA-GMA-MAPS)) capillary walls was proven. Finally, the relaxation effect as well as deformation/polarization of vesicles were demonstrated to affect OMVs electrophoretic mobility. The significance of these findings was discussed. 相似文献