SU248669A1 - Method for producing 5-halo-oxyandrostane derivatives - Google Patents

Description

The invention relates to the field of the preparation of 5p-halo-ba-oxyandrostane derivatives which may be used as biologically active substances or intermediates in the synthesis of such substances.

Br-halo-Ba-oxy-Ndrostan derivatives are proposed to be prepared on the basis of the reaction A (-drostanes derivatives with chloro-saturated or macrohumic-acid in the medium K-dialkyl-amido. products are recovered in a known manner.

Example 1. Preparation of 3-acetate 5 | 3bromine "Drostadiol-3 | 3,6a-one-17.

To a solution of 20 g of dehydroepiandrosterone acetate in 280 ml of dimethyl photomethyl imide, 47.8 g of 10% aqueous solution of perchloric acid was added at a temperature of 10 - n12 ° C and then 9.6 g dibromantine (M.M-dnbromdimetilgida-itoina). Mixture: Stir orient the temperature “above the ISC 13 for 45 min. Then, 68 ml of 9-ml, sodium sulfite, 748 ml of water and 60 ml of chloroform are added to it, and the mixture is stirred at 45 ° C for 1 hour. After cooling the reaction mass, the pizhny layer is dissolved. the latter is extracted with chloroform. Chloroform

The trials are combined and washed until neutral. The solvent is distilled off in vacuum (bath temperature 40-45 ° t) and the residue containing 5 a-bromoandrostani-diol-3p 3p, 6p-one-17 is treated with an apethoi 5 along with the desired product. Obtain 11.3 g of the desired product ((Yield 46%) with t.: Pl. 212-213 ° C, sp. Rotation {a 29.5 °

- lLJ JI (1% -. ny pacTiBop in chloroform | me). After fishing 10 hours crystallization from a mixture of acetone with chloroform (1: 1) t., Pl. purified substance 218-219 ° C and 35 °.

-Calculated,%: Br 1867

C2, Nz, 04Vg.

five

Paydeno,%: Br 18.50.

Example 2: Preparation of 3-acetate 5 | 3-chlorastrostanol-3 | 3, 6a-one-17.

To a solution of 5 g of dehydroepiandroster acetate in 1:25 ml of dimethylformamide is added, at a temperature of 4-5 ° C, 8.8 g of bleach (active chlorine content 24.8%) and 300 ml of water. The mixture is unmixed at room temperature (18-20 ° C) for 5 minutes. Then, 25 ml of acetic acid and l are added to it and the mixture is kept moving at room temperature for 30 minutes. The precipitate is filtered off and washed with water to 1; her reaction. The precipitate, which is a mixture of the target product and its 5a-bromo-B1: 5-hydroxy-isomer, is dried (the vain is treated with a mixture of methylene chloride and ether (3: 2). From a utero-after labyrinth (occurrence of electroplating agent obtain the target product With so pl. 234-237 ° C, specific rotation and 8 ° (1% solution in chloroform.me).

(Calculated,% C1 9.25.

C2lH3l04Cl.

Found,% C1 9.47.

(Example 3. Preparation of 3-acetate 17methyl-Br-bromine drostantriol-Zr, 6a, 17p.

To a solution of 3 g of 3-acetate, 17a-methyl-D, NdVO dvidiola-Zr, 17 in 52 ml of dimethylformamide, is added at a temperature of 10-12 ° C immediately with 7.2 ml of a 10% N0: th solution of chlorinated kyotota and then for 30 minutes (in four doses) 1.44 g of dibromantium. The mixture is stirred at a temperature not higher than 15 ° C for 45 minutes. Then, 10 ml of a 10% sodium sulfite solution, 208 ml of water and 9 g of chloroform are added to it and the mixture is heated for 1 hour at 45 ° C. After removing the solvent and cooling the reaction mass, the precipitate is filtered, washed with water, dried and recrystallized from a mixture of chloroformMa with acetone (1: 1). Get the target product with so pl. 149.5-150.5 ° С, specific gravity a 87.4 ° (1% solution in chloroform).

Claims (1)

Invention Formula The method of producing 5p-halo-6a-hydroxyandrostane derivatives, characterized in that the And () Androsta derivatives are subjected to Interaction with hypochlorous or hypobromous acid in N, M dialkylamides of aliphatic acids, for example, in a solution of dimethylformamide or diethylacetamide. The products obtained are isolated in a known manner.