CH210772A

CH210772A - Process for the preparation of an oxyketone ester of the androstane series.

Info

Publication number: CH210772A
Authority: CH
Inventors: Gesellschaft Fuer Chemis Basel
Original assignee: Chem Ind Basel
Priority date: 1935-06-18
Filing date: 1935-06-18
Publication date: 1940-07-31

Description

  

  Verfahren zur Darstellung eines     Ogyketonesters    der     Andr        ostanreihe.       Es wurde gefunden, dass man zu einem       Oxyketonester    der     Androstanreihe    gelangen    kann, wenn man auf ein     Androstandiol-          (3,17)-17-n-valerianat    der Formel  
EMI0001.0008     
    ein     Oxydationsmittel    einwirken lässt.

      Das so gewonnene     Androstanol-(17)-on-          (3)-valerianat    der Formel  
EMI0001.0012     
    schmilzt bei     102,5-103'.       Wie Versuche ergaben, gelingt es leicht,  den entstehenden     Oxyketonester    entweder  durch direkte     Kristallisation    oder durch Be  reitung schwer löslicher     Derivate    in reiner  Form abzuscheiden.

   Solche schwer lösliche  Derivate erhält man     zi_m    Beispiel durch Um  setzung des     Oxyketonesters    mit den üblichen    Betonreagenzien wie     .Semicarbazid,        Thio-          semicarbazid,        Hydroxylamin,        Aminoguanidin,          Phenylhydrazinen,    neutralen oder basischen       Acylhydraziden.    Durch Einwirkung     hydro-          lytisch        wirkender    Mittel werden ,

  die zwecks  Reinigung des     Oxyketonesters        hergestellten     Verbindungen     wieder    in ihre Komponenten  gespalten.           Geeignete    Oxydationsmittel sind zum  Beispiel     6wertige        Chromverbindungen    wie  Chromsäure in Eisessig, ferner Kupferoxyd.       Permanganate    und dergleichen.  



  Die erhaltene Verbindung zeichnet sich  durch Wirksamkeit an der Samenblase und  auch am     Kapaunenkamm    aus. Sie soll thera  peutische Verwendung finden.  



  <I>Beispiel:</I>  Zu einer Lösung von 3,9 g     Androstan-3-          trans-17-trans-diol-17-n-valerianat    in 50 cm'  Eisessig gibt man in der Kälte eine solche  von 1,0 g     Chromtrioxyd    in 30     em$    90%iger  Essigsäure und lässt das Ganze 24     Stunden     bei Zimmertemperatur stehen. Dann     -wird    mit  1 Liter Wasser verdünnt, das ausgefallene  Produkt abgesaugt, mit     Wasser    nach-    gewaschen und getrocknet.

   Man erhält so ein  Produkt, das nach Umfällen aus     Alkohol-          Wasser    in amorpher Form bei etwa 102,5 bis  <B>103'</B> schmilzt und sich zum Beispiel auch  über     das    schwer lösliche     Semicarbazon    rei  nigen lässt.  



  Statt von der     3-trans-Verbindung    kann  man     ebensogut    von der     3-cis-Verbindung     ausgehen.  



  An Stelle von Chromsäure kann zur Oxy  dation zum     Beispiel    auch Kupferoxyd Ver  wendung finden.



  Process for the preparation of an ogyketone ester of the Andr ostan series. It has been found that an oxyketone ester of the androstane series can be obtained if one uses an androstanediol- (3,17) -17-n-valerianate of the formula
EMI0001.0008
    allows an oxidizing agent to act.

      The androstanol- (17) -one- (3) -valerianate of the formula obtained in this way
EMI0001.0012
    melts at 102.5-103 '. As experiments have shown, it is easy to separate the resulting oxyketone ester in pure form either by direct crystallization or by preparation of poorly soluble derivatives.

   Such poorly soluble derivatives are obtained, for example, by reacting the oxyketone ester with the usual concrete reagents such as semicarbazide, thiosemicarbazide, hydroxylamine, aminoguanidine, phenylhydrazines, neutral or basic acylhydrazides. By the action of hydrolytically active agents,

  the compounds produced for the purpose of purifying the oxyketone ester are split back into their components. Suitable oxidizing agents are, for example, hexavalent chromium compounds such as chromic acid in glacial acetic acid, and also copper oxide. Permanganates and the like.



  The compound obtained is characterized by its effectiveness on the seminal vesicle and also on the capon comb. It should find therapeutic use.



  <I> Example: </I> A solution of 3.9 g of androstane-3-trans-17-trans-diol-17-n-valerianate in 50 cm 'glacial acetic acid is added in the cold to a solution of 1.0 g of chromium trioxide in 30 em $ 90% acetic acid and leave the whole thing for 24 hours at room temperature. It is then diluted with 1 liter of water, and the product which has precipitated is filtered off with suction, washed with water and dried.

   A product is thus obtained which, after reprecipitation from alcohol-water, melts in amorphous form at about 102.5 to 103 'and can also be purified, for example, using the sparingly soluble semicarbazone.



  Instead of the 3-trans connection, one can just as easily start from the 3-cis connection.



  Instead of chromic acid, for example, copper oxide can also be used for oxidation.

Claims

PATENT CLAIM: Process for the preparation of a new oxy ketone ester of the androstane series, characterized in that an androstanediol- (3.17) -17-n-valeria.nat of the formula EMI0002.0026 allows an oxidizing agent to act. The androstanol- (17) -one- (3) -n-valerianate of the formula obtained in this way EMI0002.0030 melts at <B> 102.5-103 '. </B> The compound obtained is characterized by its effectiveness on the seminal vesicle and also on the capon crest. It should find therapeutic use.

SUBClaims 1. Process according to claim, characterized in that chromic acid is used as the oxidizing agent. 2. The method according to claim, characterized in that a permanganate is used as the oxidizing agent. 3. The method according to claim, characterized in that copper oxide is used as the oxidizing agent. 4. The method according to claim, characterized in that the end product is purified by direct crystallization. 5.

Process according to claim, characterized in that the end product is reacted with. Ketone reactants and subsequent hydrolytic cleavage of the reaction product cleans.