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101.
It is shown by proton NMR and quantum chemical PCILO calculations that monothio-β-ketones in solution exist as different isomers depending on substituents, solvent and temperature. In solvents with low dielectric constants the hydrogen-bridged cis enol form predominates, and is in fast equilibrium (in the NMR scale) with nonchelated trans enol forms down to ?100°C at least. Transition enthalpies are of the order of 7–15 kJ mol?1. In compounds with R2 = Me the rotation of the Me -CS group around the neighbouring C-C- bond can be detected and the thermodynamic and kinetic parameters estimated. The reason for the slowing down of this rotation, inferred from the line broadening in NMR, is probably the stabilization of a trans isomer by interaction between the protons of the methyl group and the lone pairs of the oxygen atom. There are no indications for the presence of chelated and non-chelated enethiol isomers from the PMR studies and quantum chemical calculations performed. 相似文献
102.
A new anthraquinone glycoside, rubiayannone‐A ( 1 ), and a new coumarin, rubilatin‐A ( 2 ), together with twenty‐two known compounds were isolated and characterized from the roots of Rubia ustulata. A new anthraquinone, 2‐carbomethoxyanthraquinone ( 3 ), and rubiayannone‐A, 2‐formylanthraquinone were obtained from the roots of R. yunnanensis. The structures of those compounds were elucidated by spectroscopic methods. The antiplatelet aggregation activity of the isolated compounds 1, 4~6 were also discussed. 相似文献
103.
The reduction of prochiral ketones using chiral reducing reagents, prepared from lithium aluminum hydride and (-)-(1R, 2S, 3S, 5R)-10-anilinopinanediol (5) and (-)-(1R, 2S, 3S, 5R)-10-N-methylanilinopinanediol (6), affords chiral secondary alcohols in useful chemical yields (70 ~ 93%) but in low optical purity (8 ~ 33% ee). Modifiers 5 and 6 are synthesized from (lR)-(-)-β-pinene in three steps. 相似文献
104.
(S)-和(R)-普萘洛尔的不对称合成 总被引:3,自引:0,他引:3
普萘洛尔是一种临床上广泛使用的β受体阻断剂, 介绍了一种不对称合成(S)-和(R)-普萘洛尔的方法. 以手性Salen-CoIII催化剂水解动力学拆分外消旋环氧氯丙烷得到高光学纯度的(S)-环氧氯丙烷和(R)-3-氯-1,2-丙二醇, 以(S)-环氧氯丙烷为手性原料先水解得(S)-3-氯-1,2-丙二醇, 其与1-萘酚反应得(S)-3-(1-萘基)-丙烷-1,2-二醇, 再与氯化亚砜反应得环状亚硫酸酯, 最后和异丙胺作用得(S)-普萘洛尔, 总收率80.9%, 光学纯度大于99%; 而同样以(S)-环氧氯丙烷为手性原料直接与1-萘酚反应得(2R)-3-(1-萘氧基)-1,2-环氧丙烷, 再与异丙胺作用得(R)-普萘洛尔, 总收率74.5%, 光学纯度大于99%. 相似文献
105.
106.
A flexible approach to ethyl (3R,4S)-N-Boc-4-amino-3-hydroxy-5-phenylpentanoate (N-Boc-AHPPA-OEt), the γ-amino-β-hydroxy acid moiety of hapalosin is described. The synthetic method features a ring-opening ethanolysis of an activated N-Boc-lactam, which is obtained via a diastereoselective reductive-alkylation of (R)-malimide derivative. The flexibility of the method resides in the introduction of the alkyl side chain by Grignard reagent addition. 相似文献
107.
Changes of the rheological properties of hyaluronic acid (sodium-magnesium salt) solutions after exposure to UV radiation
indicate a vigorous decrease in their viscosity, but its still strong shear rate dependence. Whereas the presence of the singlet
oxygen sensitizer (anthracene-1-sulphonic acid) brings about a loss of shear dependence; the studied solutions show newtonian
behavior. 相似文献
108.
Shyan-Ming Yuan 《BIT Numerical Mathematics》1991,31(1):53-68
To maintain consistency on a distributed database system, a commit protocol is often employed to ensure that either all the sub-transactions of a transaction commit or all abort. Special care needs to be taken to ensure the correct functioning of a commit protocol in the face of node failures during the execution of the protocol. A protocol is said to be fault-tolerant if it properly commits or aborts, even if nodes fail.In this paper, we present a fault tolerant decentralized commit protocol which is message optimal in the absence of failures. Furthermore, the protocol (FTDCP) ensures that all sites can achieve a consistent final decision by at most 4 extra messages in the single site failure situation. 相似文献
109.
Ch. Ohn 《Letters in Mathematical Physics》1992,25(2):85-88
We obtain Zakrzewski's deformation of Fun SL(2) through the construction of a *-product on SL(2). We then give the deformation of
dual to this, as well as a Poincaré basis for both algebras.Aspirant au Fonds National belge de la Recherche Scientifique. Partially supported by EEC contract SC1-0105-C. 相似文献
110.
M. Scheunert 《Letters in Mathematical Physics》1992,24(3):173-181
It is pointed out that, for m, n 2, the naive Serre presentation corresponding to the simplest Cartan matrix of sl(m, n) does not define the Lie superalgebra sl(m, n) but a larger algebra s(m, n) of which sl(m, n) is a nontrivial quotient. The supplementary relations for the generators are found and the definition of the q-deformed universal enveloping algebra of sl(m, n) is modified accordingly. 相似文献