CH250809A - Process for the preparation of a new oxyhydrophenanthrene derivative. - Google Patents

Process for the preparation of a new oxyhydrophenanthrene derivative.

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Publication number
CH250809A
CH250809A CH250809DA CH250809A CH 250809 A CH250809 A CH 250809A CH 250809D A CH250809D A CH 250809DA CH 250809 A CH250809 A CH 250809A
Authority
CH
Switzerland
Prior art keywords
preparation
methyl
derivative
carboxylic acid
new
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 CH250809A publication Critical patent/CH250809A/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C62/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C62/30—Unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C69/757—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety

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

Description

  

  Verfahren zur Herstellung eines neuen     Oxyhydrophenanthren-Derivat>S#       Es wurde gefunden, dass man zu einem  neuen     Oxyhydrophenanthren-Derivat    gelan  gen kann, wenn man eine     1-Ä*thyliden-2-          methyl    - 7 -     benzoyloxy    -1,2,3,4 -     tetrahydro        -          phenanthren    - 2 -     carbonsäure    zwecks Über  führung der     Athylidengruppierung    in einen       Äthylrest    mit hydrierenden Mitteln be  handelt.  



  Für die     Überführung    der     Äthylidengrup-          pierung    in den     Äthylrest    kann     beispiels-          weise    die     katalytische    Hydrierung dienen.  



  Das noch nicht bekannte Endprodukt des       Verfahrens,    die 1-Äthyl-2-methyl-7-benzoyl       oxy-1,2,3,4-tetrahydro-phenanthren-2-carbon-          säure,    zeigt sowohl bei     parenteraler    als auch  bei oraler Applikation eine ausserordentlich  hohe     oestrogene    Wirkung. Es soll therapeu  tische Verwendung finden oder als Zwischen  produkt zur     Herstellung    therapeutisch ver  wendbarer Verbindungen dienen.

           Beispiel:     6     CGewiohtsteile        1-Äthyliden-2-methyl-7-          benzoyloxy    -1,2,3,4 -     tetrahydro-phenanthren-          2-carbonsäure    der Formel  
EMI0001.0031     
    (erhalten z.

   B.     aus    1-     Keto    - 2 -     methyl    - 7     -          methoxy-1,2,3,4        -letrahydro        -phenanthrenf    - 2-         carbonsäure-methylester    durch     Crrignardie-          rung    mit     Athyl-magnesiumbromid,    Wasser  abspaltung aus dem so erhaltenen     1-Äthyl-l-          oxy-    2     -methyl-7-,m thoxy-1,2,3,4-tetrahydro-          phenanthren-2-cajrb(>nsäure-methylester    vom  F.

   153 ,     Verseifung    mit     Kaliumhydroxyd     bei 200  im     Einschlussrohr    zur     1-Äthyliden-          7        -oxy    - 2 -     methyl        -1,2,3,4    -     tetrahydro    -     phen-          anthren-2-carbonsäüre    vom F. 215-216  und  anschliessende     Veresterung    mit.

       Pyridin-          Benzoy1cMorid)        schüttelt    man in einer Lö  sung von 250     Volumteilen    Wasser und 8     Ge-          wichtsteilen        Natriumhydroxyd    mit 5 Ge  wichtsteilen eines Nickelkatalysators     unter     Wasserstoff. Nach der Aufnahme der für  1     Moläquivalent    berechneten Menge Wasser  stoff wird vom Katalysator     abfiltriert    und       dass        Filtrat    mit Mineralsäure angesäuert. Man  nimmt in Äther auf, trocknet die Äther  lösung und dampft ein.

   Durch     Umkristalli-          sieren    des     Rückstandes    aus einem     Aceton-          Methylalkohol-Gemisch    erhält man die     oestro-          gen    wirksame 1-Äthyl-2-methyl-7-benzoyl       oxy-1,2,3,4-tetirahydro-phenanthren-2-carbon-          säure    der Formel  
EMI0001.0080     
    in Form farbloser     Kristalle.  



  Process for the preparation of a new oxyhydrophenanthrene derivative> S # It has been found that a new oxyhydrophenanthrene derivative can be obtained if a 1-ethylidene-2-methyl-7-benzoyloxy -1,2,3, 4 - tetrahydro - phenanthrene - 2 - carboxylic acid is treated with hydrogenating agents for the purpose of converting 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-benzoyl oxy-1,2,3,4-tetrahydro-phenanthrene-2-carboxylic acid, shows both parenteral and oral administration extraordinarily high estrogenic effect. It should find therapeutic use or serve as an intermediate product for the preparation of therapeutically ver usable compounds.

           Example: 6 parts by weight of 1-ethylidene-2-methyl-7-benzoyloxy -1,2,3,4-tetrahydro-phenanthrene-2-carboxylic acid of the formula
EMI0001.0031
    (received e.g.

   B. from 1-keto-2-methyl-7-methoxy-1,2,3,4 -letrahydro-phenanthrene-2-carboxylic acid methyl ester by Crrignardation with ethyl magnesium bromide, elimination of water from the 1-ethyl thus obtained -l- oxy- 2 -methyl-7-, m thoxy-1,2,3,4-tetrahydro- phenanthrene-2-cajrb (> methyl acid ester from F.

   153, saponification with potassium hydroxide at 200 in the containment tube to give 1-ethylidene-7-oxy-2-methyl-1,2,3,4-tetrahydro-phenanthrene-2-carboxylic acid of F. 215-216 and subsequent esterification with.

       Pyridine-Benzoy1cMorid) is shaken in a solution of 250 parts by volume of water and 8 parts by weight of sodium hydroxide with 5 parts by weight of a nickel catalyst under hydrogen. After the amount of hydrogen calculated for 1 molar equivalent has been taken up, the catalyst is filtered off and the filtrate is acidified with mineral acid. One takes up in ether, the ether solution is dried and evaporated.

   Recrystallization of the residue from an acetone-methyl alcohol mixture gives the estrogenically active 1-ethyl-2-methyl-7-benzoyl oxy-1,2,3,4-tetirahydro-phenanthrene-2-carboxylic acid the formula
EMI0001.0080
    in the form of colorless crystals.

Claims (1)

PATPNTANSPPt011 \\Verfahren zur Herstellung eines neuen Ogyhydrophenanthren-Derivates, dadurch ge kennzeichnet, dass man eine 1-Äthyliden-2- methyl - 7 - benzoylogy -1,2,3,4 - tetrahydro- phenanthren-2-carbonsäure zwecks Überfüh- rung der Äthylidengruppierung in einen Äthylrest mit hydrierenden Mitteln be handelt. PATPNTANSPPt011 \\ A process for the preparation of a new ogyhydrophenanthrene derivative, characterized in that a 1-ethylidene-2-methyl-7-benzoylogy-1,2,3,4-tetrahydrophenanthrene-2-carboxylic acid is used for the purpose of transfer the ethylidene grouping in an ethyl radical with hydrogenating agents. Das-noch nicht bekannte Endprodukt des Verfahrens, die 1-Äthyl-2-methyl-7-benzoyl ogy-1,2,ä,4-tetrahydro,phenanthren-2-carbon- säure, zeigt sowohl bei parenteraler als auch bei oraler Applikation eine ausserordentlich hohe oestrogene Wirkung. Es soll therapeu tische Verwendung finden oder als Zwischen- produkt zur Herstellung therapeutisch ver wendbarer Verbindungen dienen. The as yet unknown end product of the process, the 1-ethyl-2-methyl-7-benzoyl ogy-1,2, ä, 4-tetrahydro, phenanthrene-2-carboxylic acid, shows both parenteral and oral administration an extraordinarily high estrogenic effect. It should find therapeutic use or serve as an intermediate product for the preparation of therapeutically ver usable compounds. UNTERANSPRUCH: Verfahren gemäss Patentanspruch, da durch gekennzeichnet, dass man die Hydrie rung in Alkalilauge in Gegenwart eines Nickelkatalysators vornimmt. SUBCLAIM: Process according to claim, characterized in that the hydrogenation is carried out in alkali in the presence of a nickel catalyst.
CH250809D 1944-01-10 1944-01-10 Process for the preparation of a new oxyhydrophenanthrene derivative. CH250809A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH250809T 1944-01-10
CH242609T 1944-01-10

Publications (1)

Publication Number Publication Date
CH250809A true CH250809A (en) 1947-09-15

Family

ID=25728712

Family Applications (1)

Application Number Title Priority Date Filing Date
CH250809D CH250809A (en) 1944-01-10 1944-01-10 Process for the preparation of a new oxyhydrophenanthrene derivative.

Country Status (1)

Country Link
CH (1) CH250809A (en)

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