CH262272A - Process for the preparation of a new oxy-octahydro-phenanthrene derivative. - Google Patents

Process for the preparation of a new oxy-octahydro-phenanthrene derivative.

Info

Publication number
CH262272A
CH262272A CH262272DA CH262272A CH 262272 A CH262272 A CH 262272A CH 262272D A CH262272D A CH 262272DA CH 262272 A CH262272 A CH 262272A
Authority
CH
Switzerland
Prior art keywords
octahydro
phenanthrene
methyl
carboxylic acid
methoxy
Prior art date
Application number
Other languages
German (de)
Inventor
Aktiengesellschaft Ciba
Original Assignee
Ciba Geigy
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 Ciba Geigy filed Critical Ciba Geigy
Publication of CH262272A publication Critical patent/CH262272A/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/58—Preparation of carboxylic acid halides
    • C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

  

  <B>Verfahren</B>     zur   <B>Herstellung eines neuen</B>     Oxy-oetahydro-phenanthren-Derivates.       Es wurde gefunden, dass man zu einem  neuen     Oxy-octahydro-plienanthren-Derivat    ge  langen kann, wenn man eine     1-Äthyliden-2-          methyl-7-methoxy        -1,2,3,4,9,10,11,12-octahydro-          phenanthren-2-carbonsäure    zwecks Überfüh  rung der     Äthylidengruppierung    in einen       Äthylrest    mit hydrierenden Mitteln behandelt.  



  Für die Überführung der     Äthy        lidengrup-          pierung    in den     Äthylrest    kann beispielsweise  die katalytische Hydrierung dienen.  



  Das noch nicht bekannte Endprodukt des  Verfahrens, die     1-Äthyl-2-methyl-7-metlioxy-          1,2,3,4,9,10,11,12    -     octahydro    -     phenanthren    - 2     -          carbonsäure    vom F. 187-188 , zeigt sowohl  bei     parenteraler    als auch bei oraler Applika  tion eine ausserordentlich hohe     oestrogene     Wirkung. Es soll therapeutische Verwendung  finden oder als Zwischenprodukt zur Herstel  lung therapeutisch verwendbarer Verbindun  gen dienen.  



  <I>Beispiel:</I>  6 Gewichtsteile 1-     Äthyliden    - 2 -     methyl-7-          methoxy    -1,2,3,4,9,10,11,12 -     octahydro    -     plien-          anthren-2-carbonsäure    der Formel  
EMI0001.0028     
    (erhalten z.

   B. aus     1-Keto-2-methyl-7-methoxy-          1),2,    3, 4, 9,10,11,12 -     octahydro    -     phenanthren        -          2-carbonsäuremethy        lester    vom F.

       133-135        durch     Umsetzung    mit     Natriumacetylid,   <B>Hy-</B>  drierung der     Acety        lendreifachbindung,    Was  serabspaltung aus dem so erhaltenen     1-Äthyl-          1        -oxy-    2     -inethy        l-7-methoxy-1,2,3,4,9,10,11,

  12        -          octaliydro-plienanthren-2-        carbonsäuremethy        l-          ester    und anschliessende     Verseifung    mit     Ka-          liumhydroxyd    bei 160 ) schüttelt man bei  Raumtemperatur in einer Lösung von 1000     Vo-          lumteilen    Methanol mit 10 Gewichtsteilen eines  Platinkatalysators unter Wasserstoff. Nach be  endigter     Wasserstoffaufnahme    wird vom Ka  talysator     abfiltriert    und das Filtrat im Va  kuum verdampft.

   Man nimmt in Äther auf,  wäscht die Ätherlösung mit Wasser und  dampft sie ein. Durch     Umkristallisieren    des  Rückstandes aus einem     Aceton-Methylalkohol-          Gemisch    erhält man die     oestrogen    wirksame       1-Äthyl-2-methyl-7-methoxy        -1,2,3,4,9,10,11,12-          octahydro-phenanthren-2-carbonsäure    der For  mel  
EMI0001.0065     
    in Form farbloser Kristalle vom F. 187-188 .    Daneben wird eine     isomere    Säure vom  F. 227-229  gebildet.



  <B> Process </B> for the <B> production of a new </B> oxy-oetahydro-phenanthrene derivative. It has been found that a new oxy-octahydro-plienanthrene derivative can be obtained if a 1-ethylidene-2-methyl-7-methoxy -1,2,3,4,9,10,11,12 is used -octahydro- phenanthrene-2-carboxylic acid treated with hydrogenating agents for the purpose of transferring the ethylidene group into an ethyl radical.



  Catalytic hydrogenation, for example, can be used to convert the ethylidene group into the ethyl radical.



  The as yet unknown end product of the process, the 1-ethyl-2-methyl-7-metlioxy-1,2,3,4,9,10,11,12-octahydro-phenanthrene-2-carboxylic acid of F. 187-188 , shows an extraordinarily high estrogenic effect in both parenteral and oral application. It is intended to be used therapeutically or as an intermediate for the manufacture of therapeutically usable compounds.



  <I> Example: </I> 6 parts by weight of 1-ethylidene-2-methyl-7-methoxy -1,2,3,4,9,10,11,12-octahydro-plienanthrene-2-carboxylic acid of the formula
EMI0001.0028
    (received e.g.

   B. from 1-keto-2-methyl-7-methoxy- 1), 2, 3, 4, 9,10,11,12 - octahydro - phenanthrene - 2-carboxylic acid methyl ester from F.

       133-135 by reaction with sodium acetylide, <B> Hy- </B> dration of the acetyl triple bond, water splitting off from the 1-ethyl-1 -oxy-2-ethyl-7-methoxy-1,2,3 thus obtained , 4,9,10,11,

  12-octaliydro-plienanthrene-2-carboxylic acid methyl ester and subsequent saponification with potassium hydroxide at 160) is shaken at room temperature in a solution of 1000 parts by volume of methanol with 10 parts by weight of a platinum catalyst under hydrogen. After hydrogen uptake is complete, the catalyst is filtered off from the Ka and the filtrate is evaporated in vacuo.

   You take up in ether, wash the ethereal solution with water and evaporate it. By recrystallizing the residue from an acetone-methyl alcohol mixture, the estrogenically active 1-ethyl-2-methyl-7-methoxy -1,2,3,4,9,10,11,12-octahydro-phenanthrene-2- carboxylic acid of the formula
EMI0001.0065
    in the form of colorless crystals from F. 187-188. In addition, an isomeric acid of F. 227-229 is formed.

Claims (1)

PATENTANSPRUCH: Verfahren zur Herstellung eines neuen Oxy - octahydro - phenanthren - Derivates, da- durch gekennzeichnet, dass man eine 1-Äthyl- iden-2 -methyl - 7 - methoxy-1,2,3,4,9,10,11,12- octahydro-phenanthren-2-carbonsäure zwecks Überführung der Äthylidengruppierung in einen Äthylrest mit hydrierenden Mitteln be handelt. PATENT CLAIM: Process for the production of a new oxy-octahydro-phenanthrene derivative, characterized in that a 1-ethylidene-2-methyl-7-methoxy-1,2,3,4,9,10,11 , 12-octahydro-phenanthrene-2-carboxylic acid for the purpose of converting the ethylidene group into an ethyl radical with hydrogenating agents. Das. noch nicht bekannte Endprodukt.des Verfahrens, die 1-Äthyl-2-methyl-7-methoxy-1, 2,3,4,9,10,11,12- octaliydro-phenanthren - 2 - car- bonsäure vom F. 187-188 , zeigt sowohl bei parenteraler als auch bei oraler Applikation eine ausserordentlich hohe oestrogene Wir kung. Es soll therapeutische Verwendung fin den oder als Zwischenprodukt zur Herstel lung therapeutisch verwendbarer Verbindun gen dienen. The. as yet unknown end product of the process, the 1-ethyl-2-methyl-7-methoxy-1, 2,3,4,9,10,11,12-octaliydro-phenanthrene-2-carboxylic acid from F. 187 -188, shows an extraordinarily high estrogenic effect on both parenteral and oral administration. It is intended to be used in therapy or as an intermediate for the production of therapeutically usable compounds. D NTER.ANSPRUCH ; Verfahren gemäss Patentanspruch, dadurch gekennzeichnet, dass man die Hydrierung in Methanol in Gegenwart eines Platinkatalysa- tors vornimmt. D NTER. CLAIM; Process according to claim, characterized in that the hydrogenation is carried out in methanol in the presence of a platinum catalyst.
CH262272D 1947-04-24 1947-04-24 Process for the preparation of a new oxy-octahydro-phenanthrene derivative. CH262272A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH262272T 1947-04-24

Publications (1)

Publication Number Publication Date
CH262272A true CH262272A (en) 1949-06-30

Family

ID=4474283

Family Applications (1)

Application Number Title Priority Date Filing Date
CH262272D CH262272A (en) 1947-04-24 1947-04-24 Process for the preparation of a new oxy-octahydro-phenanthrene derivative.

Country Status (1)

Country Link
CH (1) CH262272A (en)

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