CH242994A - Process for the preparation of a new compound of the cyclopentanopolyhydro-phenanthrene series. - Google Patents

Process for the preparation of a new compound of the cyclopentanopolyhydro-phenanthrene series.

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Publication number
CH242994A
CH242994A CH242994DA CH242994A CH 242994 A CH242994 A CH 242994A CH 242994D A CH242994D A CH 242994DA CH 242994 A CH242994 A CH 242994A
Authority
CH
Switzerland
Prior art keywords
methyl ester
acetoxy
cyclopentanopolyhydro
preparation
new compound
Prior art date
Application number
Other languages
German (de)
Inventor
Reichstein Tadeus Dr Professor
Original Assignee
Reichstein Tadeus Dr Professor
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 Reichstein Tadeus Dr Professor filed Critical Reichstein Tadeus Dr Professor
Publication of CH242994A publication Critical patent/CH242994A/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J9/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J3/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, substituted in position 17 beta by one carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J5/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, substituted in position 17 beta by a chain of two carbon atoms, e.g. pregnane and substituted in position 21 by only one singly bound oxygen atom, i.e. only one oxygen bound to position 21 by a single bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J7/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of two carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J75/00—Processes for the preparation of steroids in general

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Steroid Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

  

  Verfahren zur Herstellung einer neuen     herbindung    der     Cyclopentanopolyhydro-          phenanthren-Reihe.       Es wurde gefunden, dass man zu einer im  Ring C ungesättigten Verbindung der     Cy        clo-          peritanopolyhydrophenanthren-Reihe    gelan  gen kann, wenn man einen     3a-Acetoxy-ätio-          cliolansäure-metliylester,    der im Ring C in       12-Stellung    einen zusammen mit einem be  nachbarten Wasserstoffatom     abspaltbaren          Substituenten    aufweist,

   mit diesen     Substi-          tuenten    unter Bildung einer Doppelbindung  abspaltenden Mitteln behandelt.  



  Der     12ständige,    zusammen mit einem be  nachbarten Wasserstoffatom     abspaltbare          Substituent    des Ausgangsstoffes kann eine  freie     Hydroxylgruppe    oder eine beispiels  weise durch     Carbonsäuren,    wie Essig-,     Pro-          pion-    oder     Benzoesäure,    durch     Sulfonsäuren,          Halogenwasserstoffsäuren    oder     Xanthogen-          säuren    veresterte     Hydroxylgruppe    sein.  



  Die Abspaltung dieses     Substituenten     unter Bildung einer Doppelbindung kann mit    freie     Hydroxy        lgruppe    unter der     Einwirkung     von Mineralsäuren, vorzugsweise in Lösungs  mitteln, wie Eisessig, Alkohol,     Dioxan    und  dergleichen, von     Phosphorox-#Iclilorid,        Bisul-          faten,    von Ameisensäure,     Oxalsäure,    von       Säureanhy    drillen, wie     Acetanhydrid    oder       Phosphorpentoxyd,    oder durch die Einwir  kung von Katalysatoren,

   wie Jod- oder     Car-          bonsäuresalzen,    abspalten. Eine     veresterte          Hy        droxylgruppe    wird ausser durch die ge  nannten Mittel     vorzugsweise    auch mit     :-lha-          lien,    Erdalkalien,     Carbonaten,    organischen  Basen, wie     Pyridin,        Dimethylanilin    usw., ab  gespalten.     An    Stelle oder in Kombination  mit. den genannten Mitteln lässt     sich    auch er  höhte Temperatur und/oder verminderter  Druck anwenden.

   Gegebenenfalls arbeitet  man auch in     Gegenwart    indifferenter Gase.  Statt aus     Halogenwasserstoffsäureestern    di  rekt Halogenwasserstoff abzuspalten, kann  man das Halogen auch in     bekannter    Weise      Das neue Verfahrensprodukt, der d11,12  3a-Acetoxy-ätiocholensäure-methylester vom  F. 99-100 , soll als Zwischenprodukt zur  Herstellung therapeutisch wertvoller Pro  dukte dienen.  



       Beispiel:     5 Teile     3cc-Acetoxy-12ss-tosyloxy-ätio-          Cholansäure-methylester    vom F. 145  (erhal  ten aus 3a,     12ss    -     Dioxy    -     ätiocholansäure-          methylester    vom F.

   144-145  durch partielle       Acetylierung    und Umsetzung des erhaltenen  amorphen     3a-Acetoxy-12ss-oxy-ätiocholall-          säure-methylesters    mit     Tosylchlorid    in     Pyr-          idin)    werden mit 50 Teilen     Pyridin    im Va  kuum eingeschmolzen und 40 Stunden in  siedendem     Xylol    erhitzt.

   Das     Pyridin    wird  im Vakuum     abdestilliert,    der Rückstand in  Äther aufgenommen, die ätherische Lösung  mit verdünnter     Salzsäurelösung,        Sodalösung     und Wasser gewaschen und nach dem Trock  nen über Natriumsulfat eingedampft. Durch       chromatographische    Reinigung an     Alümi-          niumoxy    d liefert der Rückstand den     d11.12_          3a-Acetoxy-ätiocholensäure-methylester,    der  aus     Petroläther    umkristallisiert lange farb  lose Nadeln vom F. 99-100  bildet.  



  An Stelle von     Pvridin        kann    z.     B.    auch       Collidin    verwendet werden.



  Process for the production of a new compound of the cyclopentanopolyhydrophenanthrene series. It has been found that a compound of the cycloperitanopolyhydrophenanthrene series which is unsaturated in the ring C can be obtained if a methyl 3a-acetoxy-etio- cliolanate, which is in the 12-position in the ring C together with a be neighboring hydrogen atom has removable substituents,

   treated with these substituents to form a double bond separating agents.



  The 12-position substituent of the starting material which can be split off together with a neighboring hydrogen atom can be a free hydroxyl group or a hydroxyl group esterified, for example, by carboxylic acids such as acetic, propionic or benzoic acid, by sulfonic acids, hydrohalic acids or xanthic acids.



  The cleavage of this substituent with the formation of a double bond can be carried out with free hydroxyl group under the action of mineral acids, preferably in solvents such as glacial acetic acid, alcohol, dioxane and the like, of phosphorus ox- # Iclilorid, bisulfates, of formic acid, oxalic acid, of acid anhy drills, such as acetic anhydride or phosphorus pentoxide, or through the action of catalysts,

   such as iodine or carbonic acid salts, split off. In addition to the agents mentioned, an esterified hydroxyl group is preferably also cleaved with: halides, alkaline earths, carbonates, organic bases such as pyridine, dimethylaniline, etc. Instead of or in combination with. the means mentioned can also be used at elevated temperature and / or reduced pressure.

   You may also work in the presence of inert gases. Instead of splitting off hydrogen halide directly from hydrohalic acid esters, the halogen can also be used in a known manner. The new process product, the d11,12 3a-acetoxy-ätiocholenic acid methyl ester of F. 99-100, is intended to serve as an intermediate for the production of therapeutically valuable products.



       Example: 5 parts of 3cc-acetoxy-12ss-tosyloxy-etio-cholanic acid methyl ester from F. 145 (obtained from 3a, 12ss - dioxy - ethiocholanic acid methyl ester from F.

   144-145 by partial acetylation and reaction of the amorphous 3a-acetoxy-12ss-oxy-ätiocholall- acid methyl ester obtained with tosyl chloride in pyridine) are melted in vacuo with 50 parts of pyridine and heated in boiling xylene for 40 hours.

   The pyridine is distilled off in vacuo, the residue is taken up in ether, the ethereal solution is washed with dilute hydrochloric acid solution, soda solution and water and, after drying, evaporated over sodium sulfate. Chromatographic purification on aluminum oxide gives the residue the d11.12_ 3a-acetoxy-etiocholenic acid methyl ester, which, when recrystallized from petroleum ether, forms long, colorless needles of 99-100 mm.



  Instead of Pvridin, z. B. Collidine can also be used.

Claims (1)

PATENTANSPRUCH: Verfahren zur Herstellung einer im Ring C ungesättigten Verbindung der Cy- elopentanopolyhydrophenanthren-Reihe, da durch gekennzeichnet, dass man einen 3a- Acetoxy-ätiocholansäure-methylester, der im Ring C in 12-Stellung einen zusammen mit einem benachbarten Wasserstoffatom abspalt- baren Substituenten aufweist, mit diesen Substituenten unter Bildung einer Doppel bindung abspaltenden Mitteln behandelt. PATENT CLAIM: A process for the production of a compound of the cyelopentanopolyhydrophenanthrene series which is unsaturated in the C ring, characterized in that a methyl 3a-acetoxy-ätiocholansäure-methyl ester, which is in the 12-position in ring C, can be split off together with an adjacent hydrogen atom Has substituents, treated with these substituents to form a double bond separating agents. Das neun Verfahrensprodukt, der Jll,12- 3a-Aeetoxy-ätiocholensäure-methylester vom F. 99-1.00 , soll als Zwischenprodukt zur Herstellung therapeutisch wertvoller Pro dukte dienen. UNTERANSPRÜCHE: 1. Verfahren nach Patentanspruch, da durch gekennzeichnet, dass man als Aus gangsstoff 3a-Acetoxy-12ss-tosyloxy-ätio- cholansäure-methvlester verwendet. \?. Verfahren nach Patentanspruch und Unteranspruch 1, dadurch gekennzeichnet, dass man den Ausgangsstoff mit Pyridin er hitzt. The nine process product, the Jll, 12-3a-ethoxy-etiocholenic acid methyl ester of F. 99-1.00, is intended to serve as an intermediate for the production of therapeutically valuable products. SUBClaims: 1. The method according to claim, characterized in that the starting material used is 3a-acetoxy-12ss-tosyloxy-ethio-cholanic acid methyl ester. \ ?. Method according to claim and dependent claim 1, characterized in that the starting material is heated with pyridine.
CH242994D 1941-03-21 1941-03-21 Process for the preparation of a new compound of the cyclopentanopolyhydro-phenanthrene series. CH242994A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH242994T 1941-03-21
CH240789T 1942-01-28

Publications (1)

Publication Number Publication Date
CH242994A true CH242994A (en) 1946-06-15

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Family Applications (1)

Application Number Title Priority Date Filing Date
CH242994D CH242994A (en) 1941-03-21 1941-03-21 Process for the preparation of a new compound of the cyclopentanopolyhydro-phenanthrene series.

Country Status (1)

Country Link
CH (1) CH242994A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2725388A (en) * 1954-09-30 1955-11-29 American Cyanamid Co Method of preparing choladienic acid esters

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2725388A (en) * 1954-09-30 1955-11-29 American Cyanamid Co Method of preparing choladienic acid esters

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