Struktur der Drevogenine. Glykoside und Aglykone, 267. Mitteilung.

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Summary. Structures for the genins of the ester glycosides of Marsdenia erecta are suggested. They are based on the behaviour in alkaline hydrolysis of these ester glycosides, their NMR. and mass spectra and ORD. data. All genins are derived from three acyl-free pregnane derivatives, i.e. drevogenin-P (l), 17B-marsdenin (3) and marsectohexol (7). The structure of 1 is known, 3 and 7 arc new compounds, i . e. 3 = 38, 88, llcr, 128, 14~-pentahydroxy-d6-pregnen-20-one and 7 = 3 8 , 88, lla, 128,14/?, 20&hexahydroxy-d6-pregnene.Formulae 13-17 were attributed to the acyl-genins A-1, A-2, A-3, A-4 and A-5, but only two of them were pure compounds, i. e . acyl-genin A-3 = 11,12-di-O-tiglyl-17~-marsdenin (15) and acyl-genin A-5 = 11,12-di-O-acetyl-marsectohexol (17). Acyl-genin A-1 is a mixture of the two esters 13af 13b derived from drevogenin-P, and similarly acyl-genin A-2 is a mixture of the esters 14a+ 14b derived from 178-marsdenin. The poorly characterised acyl-genin A-4 is most probably a mixture of the esters 16a+ 16b, also derived from 17@-marsdenin. [3]. Aus dem Gemisch der rohen Genine konnten neben ,&Sitosteryl-~-D-glucopyranosid und wenig Marsectohexol (7) 5 verschiedene krist. Praparate, die Acylgenine A1-A5, isoliert werden, von denen aber nur das Acylgenin A5 (17) rein war. A l (13) und A2 (14) bestanden jeweils aus zwei Komponenten, auch A3 (15) und A4 (16) waren kaum ganz einheitlich. -Nach alkalischer Verseifung der rohen Acylgenine konnten neben Sauren (Essigsaure, Tiglinsaure und Benzoesaure) die folgenden vier Desacylgenine in reinen Kristallen gefasst werden : 17-iso-Drevogenin-P (2), 17b-Marsdenin (3), Marsdenin (= 17~-Marsdenin) (5) und Marsectohexol (7). Diese Stoffe waren in kleinen Mengen schon vor der alkalischen Verseifung im rohen Geningemisch enthalten. Die Struktur des 17-iso-Drevogenins-P (2) ist bekannt [4]

Section: Wie Kiirzlich Berichtet [2] Enthalten Die Blatter Von Marsdunclassified

“…12). Die Acetylierung des Marsectohexols (7) verlauft also analog wie diejenige des Drevogenins-D [4], indem auch hier die llcr-standige HO-Gruppe zunachst frei bleibt.…”

Section: Wie Kiirzlich Berichtet [2] Enthalten Die Blatter Von Marsdunclassified

See 1 more Smart Citation

Glykoside von Marsdenia erecta R. Br. 2. Mitteilung: Versuche zur Strukturbestimmung der Genine. Glykoside und Aglykone, 330. Mitteilung

Saner

Stöckel

Reichstein

1972

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“…= p-Toluolsulfonsaure, Py = Pyridin, Thf = Tetrahydrofuran, To = Toluol, W = Wasser. ,, (14,15), Myristinsaure-methylester 181" (25,10), sowie drei Unbekannte mit folgenden Komponenten: 106" (3.00, sehr wenig); 106" (3,65, sehr wenig); 181" (17,0, sehr wenig). Sie waren nicht identisch rnit geradkettigen Fettsaure-methylestern der C,-C,,-Reihe sowie q,, C,, und …”

Section: '000unclassified

Die Glykoside von Marsdenia erecta R. Br. 1. Mitteilung: Isolierungen. Glykoside und Aglykone, 325. Mitteilung

Saner

Zerlentis

Stöcklin

et al. 1970

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Summary. Dried leaves of Marsdenia erecta R. Br. gave over 6% of a crude glycoside mixture, the main portion of which consisted of weakly polar material, soluble in ether or chloroform. By mild acid hydrolysis it yielded crude sugars and aglycones. The following four crist. sugars were isolated : D-cymarose, D-oleandrose and two bioses : pachybiose and marsectobiose (C,,H,,O,, new).By PC. and TLC. the presence of digitoxose, canarose, thevetose and 3-0-methyl-6-deoxyallose could be demonstrated. The crude acyl-genin mixture contained @-sitosteryl-B-D-glucopyranoside and three highly hydroxylated pregnane derivatives : drevogenin-P, 17 B-marsdenin (C,lH,,O,, new) and marsectohexol (C,,H,,O,, new), all partly esterified with acetic, tiglic and benzoic acid. Five crist. acyl-genins (Al-A5) were isolated by chromatography, but most of them still were mixtures. After alkaline hydrolysis of the crude acyl-genins 6 acyl-free compounds were obtained. 4 of them were identical with the above mentioned substances, the other two: 17-iso-drevogenin-P and marsdenin (17 m-marsdenin) are formed from drevogenin-P and 17B-marsdenin by isomerisation.

“…[2] M. EIGEN, aImmunchemie, (15. Mosbacher Kolloquium), S. 344, Springer Verlag, Berlin 1965; [3] R. CURTI L ? U. COLOMBO, J. Amer.…”

mentioning

confidence: 99%

Die Glykoside der Samen von Dregea volubilis (L.) BENTH. ex HOOK. 2. Mitt. Isolierung weiterer Drevogenine Glykoside und Aglykone, 277. Mitteilung

Sauer

Weiss

Reichstein

1966

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A total of fifteen substances were identified through thin‐layer chromatography, after mild acid hydrolysis of the chloroform extract from the seeds of Dregea volubilis (L.) BENTH. ex HOOK. Of these fifteen substances, eight (B, D, P, O; U, V, H and T) were isolated in crystalline form. Two of these were identical with the known genins drevogenin B (B) and drevogenin D (D). Drevogenin P (P) and the unknown substance O (probably a genin) were isolated for the first time. U proved to be identical with D‐cymarose, V with the biose U1 obtained from Asclepias lilacina, and H with (+)‐methyl‐pachybioside. T was not investigated (probably a sugar derivative).