DE1150073B - Process for the production of 4ªš-methyl-testan-17ª ‰ -ol-3-one-acetate - Google Patents

Description

Process for the preparation of 49-methyl-testan-17ß-ol-3-on-acetate The main patent 1117112 describes a process for the preparation of 2-monoalkyl-substituted 3-ketosteroids described, which is characterized in that 3-ketosteroids, which if desired in the molecule any against the action of the invention Alkylating agents may contain inert substituents, with alkyl halides in Reacts the presence of sodium in liquid ammonia. The alkyl group occurs here to a carbon atom of the starting steroid in a position to the keto group. This carbon atom is used throughout all of the exemplary embodiments given there the carbon atom 2.

In a further development of the inventive concept of the main patent was now found that the alkyl group under the process conditions of the main patent in certain cases instead of the carbon = atom 2 to the other, in the ca position to the 3-keto group standing carbon atom, namely to the carbon atom 4 approach can, which has also been found in already known alkylation processes. That obviously depends on the steric configuration at carbon atom 5 in the 3-ketosteroid serving as the starting material. If the carbon atom 5 is an a-position Carries hydrogen atom or if the d4 double bond starts from carbon atom 5, the alkyl group occurs on carbon atom 2, as in the examples of the main patent described. However, if the carbon atom 5 carries a ß-hydrogen atom, so, as has now been found, the alkyl group occurs under the reaction conditions of the main patent to the carbon atom 4, the spatial arrangement on the carbon atom 4 remains open for the time being.

Example In 600 ccm of liquid ammonia, after adding a trace Ferris salt added 2.76 g of sodium with stirring. After the blue color has disappeared a solution of 15 g of testan-17β-ol-3-one tetrahydropyranyl ether in 400 ccm is added Tetrahydrofuran too. After 15 hours, 10 cc of methyl iodide is left in 40 cc of tetrahydrofuran add dropwise and stir well for another 4 to 5 hours. The reaction mixture is then added on ice, acidify with acetic acid and take the precipitated product in ether on. The washed and dried ethereal solution is evaporated and the residue treated with aqueous methanolic oxalic acid solution for the purpose of pyranyl ether cleavage. The reaction product precipitated by the addition of water is converted into fractionated Filtration through alumina 40% methylation product from the unreacted starting material severed. After acetylation and chromatography, 4e-methyltestan-17ß-ol-3-one acetate is obtained therefrom. The analytically pure product melts at 134 to 135 ° C (from ethyl acetate-hexane).

Elemental analysis for CUH3403 Found .... C 76.2 0/0, H 10.05 ° / a, O 14.1 0/0; calcd .... C 76.26 0/0, H 9.89 0/0, O 13.85 0/0. The well-known e-methyl-dl-testan-17β-ol-3-one acetate, mp 153 to 154.5 ° C., is obtained from the 4e-methyl compound by bromination and customary dehydrobromination. It turns out to be identical to authentic material due to its mixed melting point.

Infrared spectrum: dl-3-keto grouping present, no substitution recognizable by the double bond.

Absorption in ultraviolet light: E230 = 8000. This proves the constitution of the 4e-methyl-testan-17ß-ol-3-one acetate produced according to the process.

Claims (1)

PATENT CLAIM: Process for the production of 4e-methyl-testan-17ß-ol-3-on-acetate according to patent 1117112, characterized in that instead of 3-keto steroids of the 5a series or of d 4-3-keto steroids testan-17ß-ol-3-one as the starting compound used and the 4e-methyl compound obtained acetylated in a known manner.