Zur Struktur der Scilliglaucosids. 56. Mitt. über Herzglykosided

Abstract

Herzglykoside [l]Summavy. The structure of scilliglaucoside, a cardiac active squill glycoside, is revised. The assignment of the new structural formula 1 is made on the basis of NMR. spectral data.Scilliglaucosid, ein hochwirksames Herzglykosid aus der roten und weissen Varietat der Meerzwiebel, Scilla (Urgifiea) maritima Baker L. [Z], soll nach unseren fruheren Untersuchungen eine a-glykosidisch verknupfte D-Glucopyranose-Einheit, entspr. Formel 2, aufweisen [3] [4] [5]. Die ungewohnliche, der KZylze'schen Regel [6] widersprechende u-Konfiguration der Zuckerbindung wurde in erster Linie aus dem stark positiven Molekularen Drehungsbeitrag des D-Glucosid-Rests abgeleitet (A [MID =

Bufadienolides and a New Lignan from the Bulbs of Urginea maritima.

“…]. In the 13 C-NMR spectrum of 6, the signals due to the aglycone moiety were very similar to that of the known compound, scilliphaeosidin 3-O-b-D-glucoside.…”

“…Compounds 13 C-NMR spectra of 19 and 22, one anomeric proton and carbon signals and two anomeric protons and carbon signals, respectively, were observed, so these compounds were thought to be monoglycoside and diglycosides. The sugar moiety of each compound was determined by acid hydrolysis as described in the experimental section.…”

“…Scillaren A (1), 4) scillirubroside (15), 5) scilliroside (16), 5) scillarenin 3-O-b-D-glucopyranoside (18), 6) 6-desacetyl-scilliroside (20), 1) scillarenin bis-rhamnopyranoside (21), 7) 5-a-4,5-dihydro-scillaren A (27), 4) proscillaridin A (28), 8) 5-a-4,5-dihydro-scillirosidin 3-O-b-D-glucopyranoside (29), 1) scillirosidin 3-Oa-L-rhamnopyranoside (30), 6) and 5-a-4,5-dihydro-scillirosidin 3-O-a-L-quinovopyranoside (33) 1) were known as bufadienolide glycosides; especially 1, 16 and 28 were major components. Scillarenin (2), 9) scillirosidin (3), 10) scilliglaucosidin (4), 11) 3-methoxy-scilliphaeosidin (5), 5-b-14-dihydroxy-bufa-3,20,22-trienolide (7), scilliglaucogenin (8), 6) scilliglaucosidone (9), 11) 3-oxo-scilliphaeosidin (10), 12) 3-episcilliglaucosidin (11), 13) 3-epi-scillarenin (12), 14) 12-epi-scilliphaeosidin (13), 6) and 14,19-dihydroxy-3-oxo-bufa-4,20,22-trienolide (31) 15) were known bufadienolides which had the absence of sugars. On the other hand, compounds 6, 14, 17, 19, 22-26 and 32 were new compounds.…”

“…Compounds 19 and 22-26 were unknown bufadienolide glycosides. The structures of these new compounds were determined by means of FAB-MS, high resolution (HR)-FAB-MS, [a] D , circular dichroism (CD), ultraviolet (UV), infrared (IR), 1 H-NMR, 13 C-NMR, nuclear Overhauser effects (NOE) and two dimensional (2D) NMR spectra.…”

“…Compound 14 would be expected to have the molecular formula C 24 H 30 O 5 , based on FAB-MS. As compared to the C-3 hydroxyl compound, scillarenin(2), 13 C-NMR, these were assigned as H-9, H-11 and C-11, respectively. So, it would seem to have the hydroxyl group at C-11.…”