STEROIDAL SAPOGENINS. VII.¹ EXPERIMENTS IN THE HECOGENIN SERIES (PART 1)

C-22 Isomeric Dihydrosapogenins from Kryptogenin

“…The two other products each being formed in an approximate yield of 10% were unknown derivatives.® We could show that these new compounds differ only in their configuration at C-22 and have the structures of a 22,26-epoxycholestane-3/3,16£-diol (IV) and a 22,26-epoxy-22isocholestane-3/3,16£-diol (V). 4 The reduction of kryptogenin diacetate under similar conditions yielded only dihydrotigogenin diacetate as previously reported.1 The infrared spectra of IV and V exhibited strong hydroxyl absorption at 3571 cm.-1 (unassociated) and at 3401 cm.-1 (associated), no carbonyl absorption, and differed decidedly in the fingerprint region. The bands characteristic for sapogenins were absent, and there was no resemblance to the infrared spectra of dihydrosapogenins.…”

“…Cholestane-35,26-diol-22-one (XVI).-A mixture of 1.0 g. of cholestane-35,26-diol-16,22-dione 3,26-diacetate 16ethylenethioketal (XIV), 4 teaspoons of Raney nickel and 150 ml. of dioxane was refluxed for 16 hr.…”

“…Found: C, 74.35;_ H, 10.08. The oxime (hydroxylamine hydrochloride, pyridineethanol, steam-bath, 4 hr.) was obtained as thin plates from dilute methanol, m.p.…”

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

“…15. Protonenvesonanzspektrum uon 38, 128-Diacetoxy-l l -oxo-5u-ataansaure-methylester (27) (Prap. H H S 48), Smp. 110-175"/126-129", CZSHSB0, (448,56) [35] an Kieselgel (SiO, OMERCK)), Korngrosse 0,05-0,20 mm) durchgefiihrt.…”

STEROIDS AND RELATED PRODUCTS: XVII. THE SYNTHESIS OF 3,9,12,20-TETRAOXYGENATED 9,12-seco-STEROIDS. PART II

“…In this publication we endeavor to show that the stereochemistry of the fusion of rings A and B indeed influences the yield of ozonolysis of a 9,11-unsaturated 12-keto steroid. I11 a first series of experiments, we transformed hecogenin acetate (IIIa), according to Djerassi's method (3), to 23t-bromo-9(11)-dehydrohecogenill acetate (IV), which we ozonized under conditions similar to those employed in our experiments in the A/B-cis series (I). The usual worlcing up of the ozonide with aqueous hydrogen peroxide gave a 52Y0 yield of acidic material.…”