Spirostan Series Research Articles

Spectra of the metastable ions on steroid sapogenins and their dihydro derivatives

Characteristic distinguishing features of the mass spectra of steroid sapogenins of the spirostan series and their dihydroderivatives are considered. The MD and B/E = const spectra of all the key ions have been studied. It has been established that the relative intensities of the metastable peaks obtained by the two methods have close values. The orders of these magnitudes are the same for monotypical fragmentation processes. The correlation between the parameters of the spectra is disturbed if a daughter of one has a number of alternative formation pathways. On the whole, the linked-scanning spectra are characteristic to the extent that they contain metastable peaks of analogous transitions possessing close parameters.

ChemInform Abstract: Hydroxylation of Steroidal 2,4‐Diene‐6‐ketones of the Stigmastane and Spirostane Series.

AbstractHydroxylation of the steroid dienones (Ia)‐(Ic) is regiospecifically effected by reaction with AgOAc and I2 in aqueous AcOH.

Steroids of the spirostan and furostan series from plants of the genus Allium. XXVI. Structure of anzurogenin and anzuroside from the collective fruits of Allium suvorovii and Allium stipitatum

A new steroid glycoside of the spirostan series, anzuroside, has been isolated from the collective fruits of the cocultivatedAllium suvorovii Rgl. andA. stipitatum Rgl. (family Liliaceae, local name “anzur”). Enzymatic cleavage of the glycoside has given the previously undescribed steroid sapogenin anzurogenic C, which has the structure of (24S, 25S)-2α,3β,5,24-tetrahydroxy-5β-spirostan-6-one. Anzuroside is the 24-O-β-D-glucopyranoside of anzurogenin C.

Steroids of the spirostan and furostan series from plants of the genus Allium. XXV. Structure of anzurogenin B from Allium suvorovii and Allium Stipitatum

A new genin of the spirostan series — anzurogenin B having the structure of 2α,5α-epoxy-(25R)-spirostan-3β,6β-diol — has been isolated form the collective fruit of the cocultivatedAllium suvorovii Rgl. andAllium stipitatum Rgl. (family Liliaceae).

Steroids of the spirostan and furostan series of plants of the Allium genus. XXIII. Structure of cepagenin and of alliospirosides C and D from Allium cepa

Two new steroid glycosides of the spirostan series have been isolated from the fruit ofAllium cepa L. (family Liliaceae): alliospirosides C and D. On the basis of chemical transformations and spectral characteristics it has been established that the aglycon of both glycosides is a new steroid sapogenin — cepagenin — having the structure of (24S,25R)-spirost-5-ene-1β,3β,24-triol. Alliospirosides C and D are cepagenin 1-O-[O-α-L-rhamnopyranosyl-(1→2)α-L-arabinopyranoside] and 1-O-[O-α-L-rhamnopyranosyl-(1→2)-O-β-D-galactopyranoside], respectively.

Steroid glycosides of the roots ofCapsicum annuum. I. The structure of capsicosides A1, B1, and C1

Three new steroid glycosides of the spirostan series — capsicosides A1, B1, and C1 — have been isolated from a methanolic extract of the roots of red pepper. In an investigation of the products of complete acid hydrolysis of these glycosides, a single aglycon — gitogenin — was identified. The complete chemical structure of each of the capsicosides has been shown with the aid of complete and partial acid hydrolysis, methylation and methanolysis, and periodate oxidation, and also by physicochemical methods of investigation.

Steroid saponins and sapogenins ofAllium. XX. Structure of karatavisoides E and F

The structures of two new steroid glycosides of the spirostan series isolated from inflorescences of the plantAllium karataviense Rgl. (family Alliaceae) — karataviosides E and F — have been shown on the basis of chemical transformations and spectral characteristics.

Steroid saponins and sapogenins ofAllium. XIX. The structure of karatavigenin C

Two new steroid glycosides of the spirostan series — karataviosides E and F — have been isolated from inflorescences ofAllium karataviense Regel. Smith degradation of these compounds has given a steroid sapogenin, karatavigenin C, which is (25S)-spirost-5-ene-2α,3β,24S-triol. Its structure was established from an analysis of spectral characteristics.

A color reaction of steroid aglycones of the spirostan series with sulfuric acid solutions

Thus, the most intense maximum with ~ = 12'10 s is observed in the reactlon of diosgenin with 96% acid at 60=C for 30 min, while c486 reaches its maximum value, of 23'10 ~, under the conditions of the reaction of diosgenin with a 72% aqueous solution of the acid in the presence of catalytic amounts (0.0001%) of Fe(III). The coloration develops at 50=C in 60 min and remains unchanged for noL less than 5 h. A callbratlon graph is linear in the range of 0.01-0.1 mmole of diosgenin in 4 ml of acid.

A new steroid glycoside, taccaoside, fromTacca cheancer

A new steroid glycoside of the spirostan series — taccaoside (I) — has been isolated from an ethanolic extract of the roots ofTacca cheancer (familyTaccaceae). An acid hydrolysate was found to contain the aglycone diosgenin (II) and the sugars D-glucose and L-rhamnose in a ratio of 1:2. By methylation and hydrolysis of the permethylate (IV) it has been established that the two terminal L-rhamnose residues are attached at C-2 and C-3 of the D-glucose molecule which, in its turn, substitutes the hydroxy group at C-3 of diosgenin. Glycoside (I) has the structure of (25R)-spirost-5-en-3β-ol 3-0-{[0-α-L-rhamnopyranosyl-(1→2)][0-α-L-rhamnopyranosyl-(1→3)]-β-D-glucopyranoside}.

Steroid saponins and sapogenins ofAllium. XV. Eruboside B fromAllium erubescens

A new steroid glycoside of the spirostan series — eruboside B (I) — has been isolated from an ethanolic extract of the bulbs ofAllium erubescens C. Koh. In an acid hydrolysate, the aglycone β-chlorogenin (II) and the sugars D-glucose and D-galactose in a ratio of 3:1 have been found. By methylation, partial hydrolysis, and oxidation the structure of the spirostanol (I) has been established as (25R)-5α-spirostan-3β,6β-diol 3-O-{[O-β-D-glucopyranosyl-(1→3)]-[O-β-D-glucopyranosyl-(1→2)]-O-β-D-glucopyranosyl-(1→4)-β-D-galactopyranoside}.

Steroid saponins and sapogenins ofAllium XIV. The structure of karatavoiside A

From a methanolic extract of the inflorescences ofAllium karataviense Rgl. we have isolated a new steroid glycoside of the spirostan series - karatavioside A, which is (25R)-spirost-5-ene-2α,3β-diol 3-0-{[0-β-D-xylopyranosyl-(1→3)-][O-β-D-glucopyranosyl-(1→2)-]-0-β-D-glucopyranosyl-(l→4)-β-D-galactopyranoside}.

The use of tert.-butyl chromate for the location of steroids on paper chromatograms.

The use of the tert.-butyl chromate reagent on paper chromatograms has been shown (i) to detect 3-hydroxy- or 3-keto-, 4- or 5-unsaturated steroids in the androstane, pregnane, cholane, cholestane, and spirostane series if followed by heating with alkali and examination for fluorescnce emission under a 360 mμ U.V. light, and (ii) to detect 17-hydroxy-20-hydroxy- or 17-hydroxy-20-ketopregnane derivatives if followed by Zimmermann's reagent for the 17-ketosteroids produced. Oestrogens gave a red colour on tert.-butyl chromate oxidation and blue fluorescence on alkali treatment.