DE659543C - Process for the preparation of monoesters of polycyclic alcohols with germ gland hormone character - Google Patents

Description

Process for the preparation of monoesters of polycyclic alcohols with gonadal hormone character. Patent 644 505 describes a process according to which the esters of saturated polycyclic alcohols with gonadal hormone character are obtained by hydrogenation of the esters of unsaturated compounds of the follicle hormone type.

It has now been found that, in the same way, by reducing the esters of the male gonad hormone of the formula C19 H30 O., as obtainable by the processes of German patents 576967, 583854 or 62o999, monoesters of polycyclic alcohols of similar constitution with gonadal hormone character are obtained.

The reduction is carried out catalytically in a manner known per se excited hydrogen or hydrogen in statu nascendi.

The monoesters of polycyclic alcohols obtained in this way are therapeutic valuable substances and can also be used as intermediate products for the extraction of gonadal hormones Connections serve.

Example i i g of hydroxyl .acetylated male gonadal hormone, obtained according to example 3 of the patent 576 967, is dissolved in zoo ccm of ethyl alcohol and after adding the same amount of a pre-reduced nickel catalyst at 170 ° and 8o to 100 atm. Pressure treated with hydrogen in a stirred autoclave. To When the uptake of hydrogen has ended, the reaction solution freed from the catalyst becomes evaporated to dryness leaving a consistent resin as the residue. From this, the 3-acetate of androstandiol can be crystallized from alcohol Isolate shape. Example a i g of that obtained according to example i of patent 583,854 Phth, as an acid ester of the male sex hormone, is present in glacial acetic acid solution of the platinum oxide catalyst according to Adam S h r i ner at room temperature with shaking hydrogenated to full saturation. The reaction solution freed from the catalyst is evaporated to dryness in vacuo and in this way the monohexahydrophthalic acid ester this corresponding diol obtained.

Example 3 i g of the acetic acid ester of trans-androsterone of the formula C19 H30 O. is dissolved in 50 cc of alcohol. To the solution, heated to 60 °, an excess of freshly prepared 3% sodium amalgam is added over the course of 1 hour with vigorous stirring. By adding small amounts of acetic acid dropwise to the reaction mixture, it is ensured that the reaction solution is always kept somewhat acidic. After the amalgam is added. is, the reaction solution is heated to 60 ° for a further hour, then poured into water .. and extracted with ether. The ethereal extract is used after treatment. rüzi @ dilute alkali lye to dryness erege-`, steams; the monoacetate of trans ATidrostandiols-3, i 7 of the formula Cis H 32O2-Example 4-ig of the propionic acid ester of dehydro-androsterone of the formula Clg H:, 8 0z is dissolved in 25 cc of propionic anhydride and at room temperature with hydrogen in the presence treated by 0.5 g of previously reduced platinum oxide catalyst with shaking or stirring. After 2 moles of hydrogen have been consumed, the hydrogenation is terminated; the catalyst is filtered off and the filtrate is poured into water and extracted with ether. The ethereal solution is then washed acid-free with dilute alkali lye and water. On evaporation, the ethereal solution gives a mixture of isomeric propionic acid esters of androstandiols of the formula C13 H32 O "which can be purified by recrystallization.

Example 5 2 g of the acetic acid ester of trans-androsterone of the formula C "H302 are dissolved in 40 cc of glacial acetic acid and at room temperature with hydrogen in the presence of 1 g of a platinum oxide catalyst prepared according to Adam S h r i ner reduced, then the glacial acetic acid is in a high vacuum at the lowest possible temperature distilled off. Bi the customary work-up of the residue the 3-acetate of trans-Androstan.diols-3, 177 is obtained.

Similarly, other esters of the male gonadal hormone can also be used Androsterone-like built-up saturated or unsaturated oxyketones of the cyclopentanopolyhydrophenanthrene series, like the stearic acid esters, the succinic acid esters, the S.alicylic acid esters, the Lactic acid esters and the like, into the corresponding monoesters of androstandiols Formula Clg H; 2 O.> be converted.

Example 6 0.5 g of platinum oxide are prereduced in 25 cc of ethyl alcohol at 70 ° with hydrogen: then one adds: a solution of 0.7 g of andros.teron benzoate iii 25 cc of alcohol and shakes the mixture at 65 to 70 ' with hydrogen, until the hydrogen uptake is 1 mole. The solution is then filtered off from the catalyst and concentrated in the heat. When the solution is cooled, androstandiol monobenzoate-3 is obtained with a melting point of 222 to 224 °.

Claims (1)

PATENT CLAIMS Process for the preparation of monoesters of polycyclic alcohols with gonadal hormone character, characterized in that the keto group in the molecule. the ester of the male gonadal hormone C, 9 H3 () 02, as obtained, for example, by the process of patents 576967, 583854 or 62o999, is reduced to the secondary alcohol group.