Glycosylation of cardenolides. VIII. Structures of the by-products of the synthesis by the orthoester method of strophanthidol rhamnosides
The by-products formed in the preparation of strophanthiodol 19-rhamnoside and 3, 19-bisrhamnoside by the orthoester method are 3β,5-dihydroxy-8,19-epoxy-5β,14β, 17α-card-20(22)-enolide and its 3-α-L-rhamnoside. 3β,5-Dihydroxy-8,19-epoxy-5β, 14α,17β-card-20(22)-enolide has been obtained by the action of a solution of HBr in nitromethane on strophanthidol.
Optische Rotationsdispersion und Konfiguration bei Cardenoliden
In accordance with the results of Weiss & ZIFFER, the ORD spectra of cardenolides with few exceptions show a distinct Cotton effect, caused by the butenolide ring. The two extrema lie at about 260 and 228 nm; the extremum at shorter wave length is very difficult to measure, and that at longer wavelength shows fine structure in dioxane. 14α,17β-cardenolides having either a hydrogen atom or a hydroxyl group at C-14 and no double bond in rings C and D show a negative Cotton effect, whereas compounds of the other three stereoisomeric types (14α,17α; 14β,17α and 14β,17β) show a positive Cotton effect. In the case of cardenolides having an oxo group, the extremum of the oxo group at shorter wavelength overlaps that of the butenolide ring at longer wavelength. In spite of this the latter extremum could still be seen distinctly in all cases investigated to date.
THE PREPARATION AND PROPERTIES OF α-D-GLUCOPYRANOSE 1,2-(ETHYL ORTHOACETATE) TRIACETATE
Crystalline ethyl and propyl 1,2-orthoacetates of α-D-glucopyranose triacetate were prepared. Conclusions are drawn regarding the chemical properties and configurations of these compounds which are based on the conformation of the 1,2-cyclic carboxonium ion believed to be formed when the substances are treated with acetic acid.