BUFADIENOLIDES .7. ABOUT THE BUFADIENOLID E COMPLEX OF RED SQUILL

Red coloured bulbs of plants of the Urginea maritima aggregate from th e northern and southern Mediterranean area were shown to exhibit diffe rent bufadienolide compositions. Therefore, the bufadienolide complex of ''red squill'' samples from Tunesia and from Sardegna was investiga ted. Twelve bufadienolides were isolated from bulbs of tetraploid squi ll from Tunesia, sixteen from tetraploid samples from Sardegna. The co mpounds were identified by means of FAB-MS, H-1-NMR, and C-13-NMR stud ies or comparison with authentic substances. Both of the samples conta ined scilliroside (14), scillarenin 3-O-beta-D-glucoside (2), proscill aridin A (1), scilliphaeosidin 3-O-beta-D-glucoside (5), scilliglaucos ide (17), scilliphaeoside (4), and 12-epi-scilliphaeoside (7); the bul bs from Tunesia contained additionally glucoscilliphaeoside (6) and th e four new bufadienolides 12-epi-glucoscilliphaeoside (10), 12 beta-hy droxyscilliglaucosidin 3-O-beta-D-glucoside (21), 12-epi-scilliphaeosi din 3-O-beta-D-glucoside (8), and 12-epi-scilliphaeosidin 3-O-alpha-L- rhamnosido-alpha-L-rhamnoside (9). In the bulbs from Sardegna scillare n A (3), gamabufotalin 3-O-alpha-L-rhamnoside (20), scilliglaucoside ( 17), scillirubrosidin 3-O-alpha-L-rhamnoside (11), scillirubroside (12 ), 12 beta-hydroxyscilliroside (15), 5 alpha-4,5-dihydroscillirosidin 3-O-alpha-L-thevetosido-beta-D-glucoside (19), and deacetylscillirosid e (8) besides the new compounds 10-carboxy-5 beta,14 beta-dihydroxybuf a-3,20,22-trienolide 5-O-beta-D-glucoside (18) and scilliglaucogenin ( 16) were found in addition. Not only quantitative but even qualitative differences in the bufadienolide pattern between the samples of the n orthern and the southern Mediterranean area were proved. By now it is not clear whether the investigated samples belong to different chemode mes of Urginea numidica or are two different species of the Urginea ma ritima aggregate.