CH211653A - Process for the preparation of a ring ketone of the cyclopentanopolyhydrophenanthrene series. - Google Patents

Process for the preparation of a ring ketone of the cyclopentanopolyhydrophenanthrene series.

Info

Publication number
CH211653A
CH211653A CH211653DA CH211653A CH 211653 A CH211653 A CH 211653A CH 211653D A CH211653D A CH 211653DA CH 211653 A CH211653 A CH 211653A
Authority
CH
Switzerland
Prior art keywords
preparation
ring
ring ketone
series
cyclopentanopolyhydrophenanthrene series
Prior art date
Application number
Other languages
German (de)
Inventor
Gesellschaft Fuer Chemis Basel
Original Assignee
Chem Ind Basel
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chem Ind Basel filed Critical Chem Ind Basel
Publication of CH211653A publication Critical patent/CH211653A/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J1/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, not substituted in position 17 beta by a carbon atom, e.g. estrane, androstane
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J75/00—Processes for the preparation of steroids in general

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Steroid Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Description

  

  Verfahren zur Darstellung eines Ringbetons der     Cyelopentanopolyhydro-          phenanthren-Reihe.       Es wurde gefunden; dass man zu einem       Ringketon    der     Cyclopentanopolybydrophen-          anthren-Reihe    gelangen kann, wenn man     d'4-          17-Äthinyl-androstendiol-(3,17)    mit Mitteln  behandelt, die geeignet sind, die freie sekun  däre     Ringcarbinolgruppe    in eine     Ketogruppe     überzuführen und die vorhandene     boppelbin-          dung    in     4,5-Stellung    zu verschieben.  



  Das so gewonnene     d', -17-Äthinyl-testo-          steron    der Formel  
EMI0001.0015     
    schmilzt bei     270-2720.     



  Die Überführung der freien     Ringcarbinol-          in    die     Ringketogruppe    kann mit für solche  Reaktionen     bekannterweise    verwendbaren    Mitteln erfolgen, beispielsweise mit Chrom  säure und Eisessig, mit     Permanganat    und  dergleichen. Es können aber auch     Carbonyl-          verbindungen    (beispielsweise     Ketone    wie Ace  ton,     Cyclohexanon)    in Gegenwart von     Metall-          alkoholaten    (z.

   B.     Aluminiumbutylaten,        -pro-          pylaten,        Magnesium-halogen-alkoholaten),    Me  talle oder Metalloxyde der Kupfer-,     Eisen-          oder    Platingruppe, gegebenenfalls unter ver  mindertem Druck, in Gegenwart     inerter    Gase       und/oder    in Kombination mit     Wasserstoff-          acceptoren,    verwendet werden.  



  Es wurde gefunden, dass überraschender  weise ein Schutz der mehrfachen     Kohlenatoff-          Kohlenatoff-bindung    in der Seitenkette unter  den für solche Oxydationen üblichen milden  Bedingungen völlig überflüssig ist. Wird die  Reaktion in neutraler Lösung ausgeführt, so  wird vorerst das     P.r-ungesättigte        Keton    er  halten. Dieses wird nachträglich durch saure  oder basische Mittel ebenfalls in das     a.p-          ungesättigte        Keton    umgelagert.

        Die neue Verbindung soll therapeutische  Verwendung finden, oder als Zwischenprodukt  zur Herstellung     therapeutisch        vervWrdbarer     Stoffe dienen.  



  <I>" Beispiel:</I>  0,5 Teile     d',E-17-Äthinyl-androstendiol-          (3,17)    werden in 10 Teile trockenem Aceton  gelöst, mit einer Lösung von 1 Teil tertiärem       Aluminium-butylat    in 40 Teilen absolutem       Toluol    versetzt und 21 Stunden unter Rück  fluss gekocht. Nach dem Abkühlen verdünnt  man mit 100 Teilen Äther, wäscht die Lö  sung mit verdünnter Mineralsäure und Wasser,  trocknet sie und verdampft das     Lösungsmittel.     Man erhält so     dr,'-17-Äthinyl-andr-osten-3-on-          17-ol    vom F.     270-272',    welches sich aus  Essigester     umkristallisieren    lässt.



  Process for the production of a ring concrete of the Cyelopentanopolyhydro- phenanthrene series. It was found; that one can get to a ring ketone of the Cyclopentanopolybydrophen- anthrene series if one treats d'4- 17-Äthynyl-androstendiol- (3,17) with agents which are suitable for converting the free secondary ring carbinol group into a keto group and to move the existing double binding to the 4.5 position.



  The thus obtained d ', -17-ethynyl testosterone of the formula
EMI0001.0015
    melts at 270-2720.



  The free ring carbinol group can be converted into the ring keto group with agents known to be useful for such reactions, for example with chromic acid and glacial acetic acid, with permanganate and the like. However, carbonyl compounds (for example ketones such as acetone, cyclohexanone) can also be used in the presence of metal alcoholates (e.g.

   B. aluminum butylates, propylates, magnesium halogen alcoholates), metals or metal oxides of the copper, iron or platinum group, optionally under reduced pressure, in the presence of inert gases and / or in combination with hydrogen acceptors will.



  It has been found that, surprisingly, protection of the multiple carbon-carbon bond in the side chain is completely superfluous under the mild conditions customary for such oxidations. If the reaction is carried out in neutral solution, the P.r-unsaturated ketone will first be kept. This is also subsequently rearranged into the a.p- unsaturated ketone by acidic or basic agents.

        The new compound should find therapeutic use or serve as an intermediate product for the production of therapeutically useful substances.



  <I> "Example: </I> 0.5 part of d ', E-17-ethynyl-androstenediol- (3.17) are dissolved in 10 parts of dry acetone, with a solution of 1 part of tertiary aluminum butoxide in 40 Parts of absolute toluene are added and the mixture is refluxed for 21 hours. After cooling, it is diluted with 100 parts of ether, the solution is washed with dilute mineral acid and water, dried and the solvent is evaporated. This gives dr, '- 17-ethynyl- andr-osten-3-on-17-ol from F. 270-272 ', which can be recrystallized from ethyl acetate.

Claims (1)

PATENTANSPRUCH: Verfahren zur Darstellung eines Ring ketons der Cyclopentanopolyhydrophenan- threnwReihe, dadurch gekennzeichnet, dass man d',6-17-Äthirjyl-androsterrdiol-(3,17) mit Mit teln behandelt, die geeignet sind, die freie sekundäre Ringcarbinolgruppe in eine Keto- gruppe überzuführen rind die vorhandene Doppelbindung in 4,5-Stellung zu verschieben. Das so gewonnene Ar,rI-17-Äthinyl-testo- sterorr der Formel EMI0002.0021 schmilzt bei 270-272 . PATENT CLAIM: Process for the preparation of a ring ketone of the cyclopentanopolyhydrophenanthene series, characterized in that d ', 6-17-Äthirjyl-androsterrdiol- (3,17) is treated with means which are suitable for converting the free secondary ring carbinol group into a keto - to transfer group to move the existing double bond to the 4,5 position. The Ar, rI-17-ethynyl-testosterorr of the formula obtained in this way EMI0002.0021 melts at 270-272. Die neue Verbindung soll therapeutische Verwendung finden, oder als Zwischenprodukt zur Herstellung thera peutisch verwendbarer Stoffe dienen. The new compound is intended to be used therapeutically or as an intermediate for the manufacture of substances that can be used therapeutically.
CH211653D 1937-07-22 1937-07-22 Process for the preparation of a ring ketone of the cyclopentanopolyhydrophenanthrene series. CH211653A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH211653T 1937-07-22

Publications (1)

Publication Number Publication Date
CH211653A true CH211653A (en) 1940-10-15

Family

ID=4447436

Family Applications (1)

Application Number Title Priority Date Filing Date
CH211653D CH211653A (en) 1937-07-22 1937-07-22 Process for the preparation of a ring ketone of the cyclopentanopolyhydrophenanthrene series.

Country Status (1)

Country Link
CH (1) CH211653A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2721871A (en) * 1954-09-13 1955-10-25 Searle & Co 17-alkyl derivatives of 19-nortestosterone
US2744122A (en) * 1951-11-22 1956-05-01 Syntex Sa delta 4-19-nor-17alpha-ethinylandrosten-17beta-ol-3-one and process
US2774777A (en) * 1952-11-12 1956-12-18 Syntex Sa 17alpha-methyl-19-nortesterone

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2744122A (en) * 1951-11-22 1956-05-01 Syntex Sa delta 4-19-nor-17alpha-ethinylandrosten-17beta-ol-3-one and process
US2774777A (en) * 1952-11-12 1956-12-18 Syntex Sa 17alpha-methyl-19-nortesterone
US2721871A (en) * 1954-09-13 1955-10-25 Searle & Co 17-alkyl derivatives of 19-nortestosterone

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