DE1034630B - Process for the preparation of 5, 16-pregnadien-1ª ‰, 3ª ‰ -diol-20-one and 5-pregnen-1ª ‰, 3ª ‰ -diol-20-one - Google Patents

Description

Process for the preparation of 5,16-pregnadien-1ß, 3ß-diol-20-one and 5-Pregnen-1 ß, 3 ß-diol-20-one The invention relates to a process for the preparation new derivatives of the Pregnan series, in particular of 5-Pregnen-1 ß, 3ß-diol-20-one and its diacetate and the 5,16-pregnadien-1 ß, 3ß-diol-20-one occurring as an intermediate.

Sannie and Lapin have in Bull. Soc. Chim. Fr., 1955, p. 1556, the preparation of the Triacetats des Ruscon, to which they assigned the following formula described from the ruscogenin. The latter is a steroid sapogenin obtained by hydrolysis of the saponins present in the roots of the little holly (Ruscus aculeatus L.). On the basis of more recent studies, in particular by D. Burn, B. Ellis and V. Petrow (Proceedings of the Chem. Soc., 1957, p. 119), the Ruscon triacetyl derivative has the following formula Hydrolysis of this compound with cleavage of the 16-position side chain could not be achieved by S an nie and L apin. Treatment with alumina only resulted in deacylation (replacing Ac in the above formula with hydrogen), and treatment with alcoholic potassium hydroxide gave a 16-methoxypregnene compound.

It has now been found that the triacetyl derivative of Ruscon for), 16-pregnadiene-lß, 3ß-diol-2d-one Can be hydrolyzed if it is in tert-butyl alcoholic solution with aqueous Potassium hydroxide treated.

It has also been found that if one applies that of Sannie and Lapin (op. a. O.) the method described does not apply to the ruscogenin, but to the mixture the isomeric genine involved in the hydrolysis of those in the roots of the little holly contained saponins (cf. S an n i e and L ap i n, Bull. Soc. Chim. Fr., 1955, S. 1552) accrue, a mixture of the isomeric Ruscontriacetate is obtained, the on treatment in tert-butyl alcoholic solution with aqueous potassium hydroxide all pass into the 5,16-pregnadiene-1 ß, 3ß-diol-20-one.

The latter compound delivers in the selective reduction preferably by catalytic hydrogenation using palladium on a support or by means of Raney nickel the crude 5-pregnen-1 ß, 3ß-diol-20-one, which is separated by separation the ketone-free fractions using Girard's reagent T, acetylation and then Deacetylation can cleanse. This gives the pure 5-pregnen-1 ß, 3ß-diol-20-one, which is an interesting intermediate for the production of valuable Represents hormones.

The following example explains the invention without restricting it. , Example . A mixture of sapogenins produced by hydrolysis of those in the roots of Ruscus aculeatus @ L. contained saponins, is after 'that of Sannie and Lapin (op. Cit.) For the production of ruscontriacetate from ruscogenin Method converted into a mixture of the isomeric Ruscontriacetate. A solution from 3 g of the triacetate mixture in -90 ecm tert-butyl alcohol is with a solution of 4.5 g of potassium hydroxide in 5.5 ccm of water are added. The reaction mixture is 3 hours kept with stirring in a water bath heated to 30 ° C. After diluting with 100 ccm of water is extracted three times with 100 cc of ether each time. The combined ether extracts are washed with water until neutral and initially by distillation under normal pressure and then under reduced pressure (15 mm Hg) for removal evaporated the tert-butyl alcohol to dryness. This gives 2 g of crude 5,16-pregnadiene-lß, 3ß-diol-20-one, its solution in 200 cc of ethyl acetate after the addition of 0.5 g of catalyst (10 ° / @ ge palladium carbon) at normal pressure and normal temperature with introduction is shaken by hydrogen. After 2 hours, 2 hydrogen atoms are absorbed and attached to the 16-position double bond. The catalyst is filtered off from, which is washed with ethyl acetate. That combined with the washing liquids The reaction mixture is evaporated to dryness in a medium vacuum.

The residue consisting of crude 5-pregnen-lß, 3ß-diol-20-one is Purified in a known manner with the aid of Girard's reagent T.

This purified product is converted into the pure substance via its diacetyl derivative, which melts at 160 to 162 ° C and has a rotation capacity of [a] "= -f-54 °. The pure 5- Pregnenlß, 3ß-diol-20-one in the form of a product which crystallizes with 1 mol of water, which converts into needles when heated at 165 to 170 ° C. and melts at 186 to 188 ° C. The rotating power is [a] δ = + 34 `.

Claims (1)

PATENT CLAIM: Process for the production of 5,16-pregnadien-1 ß, 3ß-diol-20-one and 5-pregnen-1 ß, 3ß-diol-20-one, characterized in that one ruscontriacetate or a mixture of isomeric ruscontriacetates hydrolyzed in tert-butyl alcoholic solution with aqueous potassium hydroxide and, if appropriate, the 5,16-pregnadiene-lß, 3ß-diol-20-one thus obtained is catalytically hydrogenated in a known manner.