Drevogenin A und Drevogenin B,zusätzlicher Strukturbeweis. Glykoside und Aglykone, 306. Mitteilung

Drevogenin B is shown to be 11-O-acetyl-drevogenin P. The earlier derived structure for drevogenin A (11-O-acetyl-drevogenin P) is further confirmed by conversion of 3-O-acetyl-drevogenin A.     

Alloglaucotoxigenin,Strukturbestimmung Glykoside und Aglykone, 280. Mitteilung

The structure of alloglaucotoxigenin is shown to be that of 3β, 14β, 15β-trihydroxy-19-oxo-5α-carda-20:22-enolide (IV) in the following way: The 19-oxo group could be eliminated by reduction of the corresponding mercaptal. The structure of the resulting 3β, 14β, 15β-trihydroxy-5α-carda-20:22-enolide, obtained in the acetylated form, was established through degradation and through partial synthesis by treatment of Δ¹⁴-anhydro-uzarigenin (XIII) with osmium tetroxide. The isomeric 3β,14α, 15α-trihydroxy-cardenolide was also formed in large quantities. The substance XI showed in its optical rotatory dispersion curve a positive, and substance XIV a negative COTTON effect.     

Adigosid,Strukturbestimmung Glykoside und Aglykone, 282. Mitteilung

This publication reports the preparative isolation of adigoside from the seeds of Nerium oleander L. with a yield of 250 mg crystalline adigoside per kilogram of seeds. Mild acid hydrolysis of adigoside gave crystalline D -diginose ( 8 ) and amorphous adigenin ( 6 ), which in turn gave a crystalline mono-O-acetyl derivative 7. With the aid of physical methods, degradative reactions and partial synthesis of 7 , the structure of adigenin was proved to be that of 16-O-isovaleryl-gitoxigenin. On the basis of molecular rotation it was shown that the sugar in adigoside ( 2 ), in accordance with the KLYNE Rule, is bound in the β-D -pyranosidic form. Adigoside showed no (or at the most very weak) digitalis type activity on the cat. This lack of activity must be due to the esterification of the 16-hydroxyl group by isovaleric acid, as it is known that an acetyl residue in the same position enhances rather than lowers the activity of 16β-hydroxy-cardenolides.     

Gymnemagenin,Struktur und O-Isopropylidenderivate Glykoside und Aglykone. 313. Mitteilung

Several O-isopropylidene derivatives of gymnemagenin ( 5 ), a hexahydroxytriterpene from the leaves of Gymnema sylvestre R. Br. have been prepared, which may perhaps be useful to correlate gymnemagenin with other triterpenes. From the data obtained we conclude that gymnemagenin is 3β, 16β, 21β, 22α, 23, 28-hexahydroxy-olean-12-ene.     

Stapelogenin,vermutliche Struktur. Glykoside und Aglykone, 276. Mitteilung

Stapelogenin, C₂₁H₃₀O₄, shows a double bond and two hydroxyl groups which can be acetylated. On the grounds of UV.-, IR.-, and NMR-spectra as well as mass spectra, the probable structure is that of a 3β, 12β-dihydroxy-(18, 20β), (14β, 20α)-diepoxy-Δ⁵-pregnene ( 1 ). The exact position of the hydroxyl group, assumed to be 12β, is particularly unsure, as it could also be situated 11α- or 12α-position.     

Sarverogenin,vermutliche Struktur. Glykoside und Aglykone, 314. Mitteilung

Sarverogenin is most probably a 3β, 11β, 14β-trihydroxy-7, 8β-epoxy-12-oxo-5β-card-(20:22)-enolide ( 3 ). This follows from IR., NMR., and mass spectra together with former chemical results.     

Gymnemagenin,vermutliche struktur Glykoside und Aglykone, 289. Mitteilung

Gymnemagenin, the aglycone obtained from gymnemic acid by fermentative degradation and alkaline hydrolysis, is probably a new hexahydroxy-triterpene. The proposed structures are derived mainly from data obtained by physical methods. Gymnemagenin is probably a 3β,15α(or 16β), 21β,22α,23,28- or 3β,15α,16β,21β(or 22α), 23,28-hexahydroxy-olean-12-ene. Further experimental information is necessary for decision concerning the correct structure.     

Die vermutliche Struktur der Anodendroside. Glykoside und Aglykone, 331. Mitteilung

Five crystalline compounds (anodendrosides) have been isolated from Anodendron paniculatum (Roxb.)A. DC. (Apocynaceae). They represent glycosides containing unusual sugars. Tentative structures for anodendroside-A ( 155 ), ?E₁ ( 3 ), ?E₂ ( 84 ), ?F ( 144 ) and ?G ( 115 ) are now presented. These structures are based on UV., IR., but mostly on high resolution mass spectra. NMR.-spectra could be performed with A, O-acetyl-E₂ and O-acetyl-G, which are in good agreement with the suggested structures. The unusual methylendioxy group postulated in the sugar moiety of A, E₁ and E₂ was also established by chemical methods, yielding approximately 1 Mol. equiv. of formaldehyde after acid hydrolysis of anodendroside-E₂.     

Die Glykoside Vincetoxicum hirundinaria MEDIKUS. 3. Mitteilung: Struktur von Hirundigenin und Anhydrohirundigenin. Glykoside und Aglykone, 318. Mitteilung

Hirundigenin can easily be converted into anhydrohirundigenin by thermal dehydration. Both substances are stable to alkali but unstable under acid conditions. Dehydrogenation of anhydrohirundigenin, using selenium at 310°, gave a mixture of 2-methylphenanthrene ( 29 ), 1, 2-dimethyl-phenanthro [1,2-b] furan ( 30 ) and 1-ethyl-2-methyl-phenanthro [1,2-b] furan ( 32 ), all of which could be isolated in crystalline form. The last two substances are new and their structures were confirmed by synthesis. Through these results, as well as by further reactions and spectra, it could be shown that hirundigenin and anhydrohirundigenin are 16-methyl-15-oxapregnane derivatives, further, that they have two epoxide rings and that they probably have the structures 7 and 11. These structures were proved by O. Kennard et. al. through X-ray studies of p-bromobenzoyl-anhydrohirundigenin ( 13 ). As far as we know, 15-oxasteroids had not yet been found in nature.     

Nigrescigenin,Identifizierung mit Sarmentosigenin A Glykoside und Aglykone, 281. Mitteilung

“Sarmentosigenin A” has been identified with nigrescigenin. The latter is the older and thus valid name for this 3β, 5β, 11α, 14β-tetrahydroxy-19-oxo-card-20:22-enolide.     

Die Glykoside der Wurzeln von Xysmalobium dilatatum WEIMARCK. 1. Mitteilung: Isolierungen. Glykoside und Aglykone, 327. Mitteilung

The roots of Xysmalobium dilatatum Weimarck contain uzarin and xysmalorin as major glycosides. The same two compounds are also present as main components in the glycoside mixture from the roots of Xysmalobium undulatum. In addition to that, X. dilatatum also contains appreciable amounts of pregnane derivatives, linked to 2-deoxy-sugars. Four such xanthydrolpositive compounds (the dilatoides A, B, C and D) have been isolated in amorphous but pure or nearly pure form; they have not been detected in the roots of X. undulatum.     

Die Glykoside der Samen von Stapelia gigantea N. E. Br. Glykoside und Aglykone, 275. Mitteilung

The seeds of Stapelia gigantea are very rich in ester glycosides (ca. 5,9%). Mild acid hydrolysis gave a mixture of sugars which, after paper chromatography and electrophoresis, was found to be probably composed of cymarose, oleandrose, digitoxose, arabino-2,6-dideoxyhexose (= canarose) and pachybiose. The mixture of the raw genins gave after alkaline hydrolysis a mixture of about nine deacyl genins (C, D, E, F1, F2, F3, G, H, J); the acids split off during hydrolysis were not identified. The nine deacyl genins are probably closely related pregnane derivatives. The main component (E), C₂₁H₃₀O₄, was obtained in crystalline state, and was named stapelogenin. Its probable structure is reported in the following publication.     

Die Glykoside der Wurzeln von Xysmalobium dilatatum Weimarck. 2. Mitteilung: Teilstruktur der Dilatoside. Glykoside und Aglykone, 328. Mitteilung

The four dilatosides A, B, C and D (ester glycosides isolated from Xysmalobium dilatatum) differ from each other only in the sugar portion. They all contain the same aglycone: 12-O-acetyl-17-isolineolone (=12-O-acetyl-17-isodeacyl-cynanchogenin) ( 6 ). Its mass spectrum is discussed. In dilatoside A ( 1 ) three molecules of D -oleandrose ( 7 ) are linked to this aglycone, in dilatoside B ( 2 ) one D -canarose ( 8 ) and two oleandrose units, in dilatoside C ( 3 ) two canarose and three oleandrose, and in dilatoside D ( 4 ) probably three canarose and two oleandrose units.     

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

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 ( 1 ), 17 β-marsdenin ( 3 ) and marsectohexol ( 7 ). The structure of 1 is known, 3 and 7 are new compounds, i.e. 3 = 3β,8β,11α,12β,14β-pentahydroxy-Δ⁵-pregnen-20-one and 7 = 3β,8β,11α,12β,14β,20ξ-hexahydroxy-Δ⁵-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-17β-marsdenin ( 15 ) and acyl-genin A-5 = 11,12-di-O-acetyl-marsectohexoi ( 17 ). Acyl-genin A-1 is a mixture of the two esters 13a + 13b derived from drevogenin-P, and similarly acyl-genin A-2 is a mixture of the esters 14a + 14b derived from 17β-marsdenin. The poorly characterised acyl-genin A-4 is most probably a mixture of the esters 16a + 16b , also derived from 17β-marsdenin.     

Die Struktur der Drevogenine. 2. Mitteilung Struktur von Drevogenin P. Glykoside und Aglykone, 278. Mitteilung

Drevogenin A was converted in several steps (acetylation, hydrogenation, dehydration, hydrogenation, the haloform reaction and energetic alkaline hydrolysis) into 3β, 11α, 12β-trihydroxy-5α-etianic acid, which could be characterised by its crystalline methyl ester ( 15 ) and its tri-O-acetyl methyl ester ( 16 ). The same acid was obtained by partial synthesis starting from hecogenin. Taking into consideration earlier results [1], the structure of drevogenin P is proved to be 3β, 11α, 12β, 14β-tetrahydroxy-20-oxo-Δ⁵-pregnene ( 7 ). Energetic hydrolysis of dihydro-3-O-acetyldrevogenin A gave a mixture of 17αH- and 17βH-desacyl-kondurangogenin A, which were obtained in crystalline form after separation by chromatography. The only difference between the basic structures of the drevogenins and kondurangogenin A is the presence of a double bond in the 5-position in the former.     

Die Struktur der Drevogenine. 3. Mitteilung Struktur von Drevogenin A,B und D. Glykoside und Aglykone, 279. Mitteilung

The treatment of drevogenin P with isovaleryl chloride in pyridine gave an amorphous 3,12-di-O-isovaleryl-drevogenin P ( 4 ), which, on energetic acetylation, was converted into 3-O-isovaleryl-drevogenin A ( 5 ). This could be isolated in crystalline form and was converted through mild alkaline hydrolysis into drevogenin A. Hence drevogenin A could be classified as 11-O-acetyl-12-O-isovaleryl-drevogenin P. Indirectly, the structure of drevogenin B could be deduced to be most probably that of 11α-mono-O-acetyl-drevogenin P. Some details of the earlier given structures [1] are corrected here. Drevogenin D has an 11α-hydroxyl group.     

Die Glykoside der Wurzeln von Kanahia laniflora (FORSSK.) R. BR. 1. Mitteilung: Isolierungen. Glykoside und Aglykone, 299. Mitteilung

The roots of Kanahia laniflora (FORSSK .) R. BR . contain, in addition to small quantities of cardenolides, a large amount of ester glycosides which are difficulty separable from one another. However, two of these ester glycosides were obtained in a nearly pure form. The crude mixture of ester glycosides, after mild acidic hydrolysis, gave a mixture of acyl-genins and three sugars: D -oleandrose, D -digitoxose and D-canarose, all of which were obtained in crystalline form. Acetic acid, benzoic acid and another unidentified acid were obtained on alkaline hydrolysis of the mixture of acyl-genins along with 17-isolineolon, lineolon, deacetylmetaplexigenin and a small amount of sarcostin-ketone. Besides these known genins, three probably new genins (α, τ, λ) were obtained in small, but crystalline amounts.     

Die Glykoside der Wurzeln von Glossostelma carsoni (N. E. BR.) BULLOCK. Glykoside und Aglykone, 297. Mitteilung

Pentacyclic triterpenes, sterols, cardenolides and pregnane derivatives could be identified in extracts from roots of Glossostelma carsoni (N.E. BR .) Bullock. From the first group, the following substances could be isolated in crystalline form: β-amyrin, lupeol, their 3-O-acetyl derivatives, and 3-O-isovaleryl-β-amyrin. The sterols were isolated in the form of two mixed but crystalline fractions. The less polar fraction was shown to be a mixture of β-sitosterol, campesterol, stigmasterol, and cholesterol (stereoisomers are not excluded); the more polar fraction is probably a mixture of monohydroxy derivatives of the four above mentioned sterols.     

Die Cardenolide und Pregnan-Glykoside der Wurzeln von Asclepias lilacina WEIMARCK. I. Isolierungen Glykoside und Aglykone, 290. Mitteilung

The dried roots of Asclepias lilacina contain ca. 14% glykosides, in which both cardenolides and ester glycosides of pregnane derivatives are present, the latter predominating. Uzarigenin, coroglaucigenin, and their corresponding glycosides ascleposide and frugoside, resp., were shown to be present; of these four, uzarigenin was isolated in crystalline form. The ester glycosides, some of which could be isolated in a crystalline state, are predominantly composed of the aglycones 20-O-acetyl-12-O-benzoyl-sarcostin and 12,20-di-O-benzoyl-sarcostin, besides which esters of desacetyl-metaplexigenin, lineolon, and dihydrosarcostin are also present. These aglycones are mostly attached to various trisaccharides which are composed of at least two 2-deoxy-sugar residues. Mild acid hydrolysis gave, besides the genins, 7 sugars, namely cymarose, oleandrose, digitoxose, 3-O-methyl-6-deoxy-D-allose (U3), as well as 3 unknown sugars U1, U2 and U5 which are probably disaccharides. U1 and U2 were isolated in crystalline form; they are isomeric and have been named asclepobiose and lilacinobiose; they are probably composed of units similar to those in the isomeric pachybiose.