Die Glykoside der Blätter von Digitalis canariensis L., var. isabelliana (WEBB) LINDINGER

Abstract

1607d,l-18-Hydroxy-corticosteronr (XII, XIII), the d-enantiomer (I) of which is probably a direct biogenetic precursor of aldosterone (I1 a, b), has been prepared. The synthesis leads from the trihydroxy-diketal IV to the diacetate VI, in which the ketal groups could be split with a mixture of perchloric and acetic acid. The diacetoxydiketone I X thus obtained was hydrolysed under carefully controlled alkaline conditions to yield the 18-monoacetate XI or the free d,l-18-hydroxy-corticosterone (XII). The latter compound exists, however, predominantly in the form of the (20-+18)cyclohemiketal XIII, a conclusion reached from its infrared absorption spectrum and the comparatively slow reduction of tetrazolium salt.By degradation of XI11 with periodic acid the d,l-lactone XV was obtained, which is the racemate corresponding to the optically active compound ((A 5 9~, isolated from hog adrenal extracts.By treating the lip, 18-dihydroxy-diketals IV and V with aqueous acetic acid, in addition to ketal cleavage intramolecular etherification between the llgand 18hydroxy groups took place andd,l-18-desoxy-aldosterone (d,l-llp, 18-oxido-cortexone) (VII) and its 21-0-acetyl derivative VIII were formed, respectively.Forschungslaboratorien der CIBA AKTIENGESELLSCHAFT, Basel, Pharmazeutische Abteilung

Die Glykoside der Blätter von Isoplexis isabelliana (WEBB) MASF.. 3. Mitteilung

“…zu 400 ml. [1][2][3][4][5][6][7][8][9] Aus den oben erwahnten 67 g des Getnisches der Monoside wurden insgesamt erhalten (jeweils aus An kristallisiert): 60 mg Substanz tHF7a (feine Nadelchen) vom 90 mg Substunz t H F 2 r (Nadelchen) vom Smp. , Chf und Chf-Me-(99: l)] gaben 220 mg Eindampfriickstande, die verworfen wurden.…”

Natural Products Isolated from Plants of the Canary Islands

“…The mixture of glycosides yielded the diglycosides glucoevatromonoside, cheiroside A and 'digitalinum verum' together with other derivatives of digitoxigenin, uzarigenin and xysmalogenin directly bound to 6-deoxy-D-glucose, its 2-0-acetyl compound, D-canarose or D-digitoxose and terminating by a glucose unit. The C 21 -steroid glycosides digifolein, diginin, lanafolein, 141X.-digipronin and strospeside and the genins y-digiprogenin, purpnigenin, 3~, 14 ~-dihydroxypregn-5-en-20-one, 3~, 14 ~-dihydroxypregn-5-en-15,20-dione and its digitoxoside were also found as well as the spirostan sapogenins tigogenin and neotigogenin (Breton & Gonzalez 1960b;Rees et al 1961a;Pavanaram et al 1963f;Freitag et al 1967g).…”

Stoffwechselprodukte von Mikroorganismen 73. Mitteilung [1] Chlorothricin und Des‐chlorothoricin

“…Die 2-Desoxy-D-rhamnose (= D-Chromose C = ~-0livose) wurde schon fruher mehrmals als Baustein anderer Antibiotica aus Actinomyceten nachgewiesen [5] [6] 171, u. a. im Avilamycin [8] ebenfalls mit einer chlorhaltigen aromatischen Carbonsaure verestert. Unter dem Namen Canarose ist sie als Baustein von Digitalis-Glykosiden mehrmals beschrieben [9] und auch synthetisch hergestellt worden [lo]. (3,76).…”