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121.
Sandrine Henry De Hassonville Bruno Perly Géraldine Piel Thierry Van Hees Valéry Barillaro Pascal Bertholet Luc Delattre Brigitte Evrard 《Journal of inclusion phenomena and macrocyclic chemistry》2002,44(1-4):289-292
Cyproterone acetate (CPA) is a steroidal antiandrogen with a progestogenic activity. Given that this molecule has a very poor water solubility (2.1 g/mL), different cyclodextrins (CDs) were tested to form inclusion complexes and to increase solubility. Two different techniques were compared to study the affinity between CPA and CDs: phase-solubility studies and NMR spectroscopy. The stoichiometry and the stability constant could be determined for most complexes with the aid of phase-solubility studies. The greatest increase in solubility was achieved with the methylated -CDs, but hydroxypropylated - and -CDs also gave enhanced solubilities. 1H-NMR studies showed a solubility increase similar to that found with phase-solubility studies. The proof of inclusion in the2,6-dimethyl--CD (DIMEB) was shown by 1H-NMR and t-ROESY spectra. 相似文献
122.
Ivo Lakomy Daniel Sarbach Bruno Traber Christoph Arm Daniel Zuber Hanspeter Pfander Klaus Noack 《Helvetica chimica acta》1997,80(2):472-486
Starting from (R)-3-hydroxybutyric acid ((R)- 10 ) the C45- and C50-carotenoids (all-E,2S,2′S)-bacterioruberm ( 1 ), (all-E,2S,2′S)-monoanhydrobacterioruberin ( 2 ), (all-E,2S,2′S)-bisanhydrobacterioruberin ( 3 ), (all-E,2R,2′R)-3,4,3′,4′-tetrahydrobisanhydrobacterioruberin ( 5 ), and (all-E,S)-2-isopentenyl-3,4-dehydrorhodopin ( 6 ) were synthesized. By comparison of the chiroptical data of the natural and the synthetic compounds, the (2S)- and (2′S)-configuration of the natural products 1–3 and 6 was established. 相似文献
123.
The α-D -allo-diol 9 possesses an intramolecular H-bond (HO? C(3) to O? C(1)) in solution and in the solid state (Fig. 2). In solution, it exists as a mixture of the tautomers 9a and 9b (Fig. 3), which possess a bifurcated H-bond, connecting HO? C(2) with both O? C(1) and O? C(3). In addition, 9a possesses the same intramolecular H-bond as in the solid state, while 9b is characterized by an intramolecular H-bond between HO? C(3) and O? C(4). In solution, the β-D -anomer 12 is also a mixture of tautomers, 12a and presumably a dimer. The H-bonding in 9 and 12 is evidenced by their IR and 1H-NMR spectra and by a comparison with those of 3–8, 10 , and 11 . The expected regioselectivity of glycosidation of 9 and 12 by the diazirine 1 or the trichloroacetimidate 2 is discussed on the basis of the relative degree of acidity/nucleophilicity of individual OH groups, as governed by H-bonding. Additional factors determining the regioselectivity of glycosidation by 1 are the direction of carbene approach/proton transfer by H-bonded OH groups, and the stereoelectronic control of both the proton transfer to the alkoxy-alkyl carbene (in the σ-plane) and the combination of the thereby formed ions (π-plane of the oxycarbenium ion). Glycosidation of 9 by the diazirine 1 or the trichloroacetimidate 2 proceeded in good yields (75–94%) and with high regioselectivity. Glycosidation of 9 and 12 by 1 or 2 gave mixtures of the disaccharides 14–17 and 18–21 , respectively (Scheme 2). As expected, glycosidation of 12 by 1 or by 2 gave a nearly 1:1 mixture of regioisomers and a slight preference for the β-D -anomers (Table 4). Glycosidation of the α-D -anomer 9 gave mostly the 1,3-linked disaccharides 16 and 17 (α-D β-D ) along with the 1,2-linked disaccharides 14 and 15 (α-D < β-D , 1,2-/1,3-linked glycosides ca. 1:4), except in THF and at low temperature, where the β-D -configurated 1,2-linked disaccharide 15 is predominantly formed. Similarly, glycosidation of 9 with 2 yielded mainly the 1,3-linked disaccharides (1,2-/1,3-linked products ca. 1:3 and α-D /β-D ca. 1:4). Yields and selectivity depend upon the solvent and the temperature. The regioselectivity and the unexpected stereoselectivity of the glycosidation of 9 by 1 evidences the combined effect of the above mentioned factors, which also explain the lack of regio-complementarity in the glycosidation of 9 by 1 and by 2 (Scheme 3). THF solvates the intermediate oxycarbenium ion, as evidenced by the strong influence of this solvent on the regio- and stereoselectivity, particularly at low temperatures, where kinetic control leads to a stereoelectronically preferred axial attack of THF on the oxycarbenium ion. 相似文献
124.
Ngouela S Ndjakou BL Tchamo DN Zelefack F Tsamo E Connolly JD 《Natural product research》2005,19(1):23-27
A prenylated xanthone has been isolated from the seeds of Symphonia globulifera together with the known compounds sitosterol and oleanolic acid. The structure of the new compound was elucidated by spectroscopic methods. 相似文献
125.
Ngouela S Zelefack F Lenta BN Ngouamegne ET Tchamo DN Tsamo E Connolly JD 《Natural product research》2005,19(7):685-688
A xanthone derivative, 3,6,7-trihydroxy-1-methoxyxanthone has been isolated from the stem bark of Allanblackia monticola together with other known compounds, 2,6-dihydroxy-1-methoxyxanthone, allanxanthone A, epicathechin and oleanolic acid acetate. The structure of the new compound was elucidated by spectroscopic methods. 相似文献
126.
New Phellandrene Derivatives from the Root Oil of Angelica archangelica L . 2-Nitro-1,5-p-menthadiene ( 5 ), trans- and cis-6-nitro-1(7), 2-p-menthadiene ( 6 and 7 ), trans-1(7), 5-p-menthadien-2-yl acetate ( 9 ) and a formal phellandrene derivative, 7-isopropyl-5-methyl-5-bicyclo [2.2.2]octen-2-one ( 16 ), have been identified in the root oil of Angelica archangelica L . Starting from (?)-(R)-α-phellandrene ( 1 ) (R)- 5 , (4R, 6S)- 6 /(4R, 6R)- 7 , (2S, 4R)- 9 and (1R, 4R, 7R)- 16 as well as (2S, 4R)- 11 , (2R, 4R)- 12 and (2R, 4R)- 10 have been prepared. 相似文献
127.
Enamino- and Halogenoacetylenic sugars Traitment of an aldehydosugar ( 1 ) with secondary amines gave in an essentially quantitative yield the expected enamines ( 4–6 ). Chloro- and bromo-acetylenic sugars ( 11–14 ) were obtained in good yields by reacting with lithium methylphenylamide the corresponding gem-dihalo-olefinic sugars ( 7–10 ), whereas a Z-gem-fluoro-enamine ( 17 ) was formed when the difluoro-olefinic sugar 15 was submitted to the same reaction. The fluoro-enamine 17 is a useful synthetic intermediate allowing the preparation of several kinds of C-glycosylic compounds bearing heterocycles like isoxazole, chromone or coumarin. 相似文献
128.
129.
Chryss Chryssomalakos Bernhard Drabant Michael Schlieker Wolfgang Weich Bruno Zumino 《Communications in Mathematical Physics》1992,147(3):635-646
Using previous results we construct theq-analogues of the left invariant vector fields of the quantum enveloping algebra corresponding to the complex Lie algebras of typeA
n–1
,B
n
,C
n
, andD
n
. These quantum vector fields are functionals over the complex quantum groupA. In the special caseA
1 it is shown that this Hopf algebra coincides withU
q
sl(2, ). 相似文献
130.
A series of new esters of lutein ( 1a ) have been prepared with the aim of confirming the structure of lutein via an X‐ray crystal‐structure analysis. Although well crystallized, only one of the derivatives, the (?)‐(1R)‐menthyl carbonate ( 1i ) proved to be useful for a complete structure analysis. The same derivative of zeaxanthin ( 2a ) also allowed its crystal structure to be determined. Both analyses represent the first successful X‐ray crystal structure analyses of the most important xanthophylls. At the same time, they confirm both the constitution and absolute configuration of 1a and 2a that had been deduced earlier by classical methods. 相似文献