CH250808A - 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
CH250808A
CH250808A CH250808DA CH250808A CH 250808 A CH250808 A CH 250808A CH 250808D A CH250808D A CH 250808DA CH 250808 A CH250808 A CH 250808A
Authority
CH
Switzerland
Prior art keywords
preparation
methyl
carboxylic acid
phenanthrene
derivative
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 CH250808A publication Critical patent/CH250808A/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

Landscapes

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

Description

  

  Verfahren zur     HerstellunLr        eines    neuen     Oxvhvdronhenanthren-Derivates¯       Es wurde gefunden, dass man zu einem  neuen     Ogyhydrophenanthren-Derivat    gelan  gen kann, wenn man eine     1-Äthyliden-2-          methyl    - 7 -     propionylogyy    -1,2,3,4 -     tetrahydro-          phenanthren-2-carbonsäure    zwecks     Ilberfüh-          rung    der     Äthylidengruppierung    in einen       Äthylrest    mit hydrierenden Mitteln behan  delt.  



  Für die Überführung der     Ä.thylidengrup-          pierung    in den     Äthylrest    kann beispielsweise  die katalytische Hydrierung dienen.  



  Das noch nicht     bekannte    Endprodukt des  Verfahrens.,     diel-Äthyl-2-methyl-7-propionyl-          ogy-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 Gewichtsteile     1-Äthyliden-2-methyl-7-          propionylogy-1,2,        3,4-tetrahydr        o-phenanthren-          2-carbonsäure    der     Formel     
EMI0001.0035     
    (erhalten     z.    B.

   aus 1-Keto-2-methyl-7-meth  oxy-1,2,3,4-tetrahydro-phenanthren-2-carbon-         säure-methylester    durch     Grignardierung    mit       Äthyl-magnesiumbromid,    Wasserabspaltung  aus dem so erhaltenen     1-Äthyl-l-ogy-2-          methyl    - 7 -     methogy    -1,     2,3,4=tetrahydro-phen-          anthren    - 2 -     carbonsäure    -     methylester    vom  F.

   153 ,     Verseifung    mit     Kaliumhydrogyd    bei  200  im     Einschlussrohr    zur     1-Äthyliden-7-          ogy    - 2 -     methyl    -1,2,3,4 -     tetrahydeo    -     phen-          anthren-2-carbonsäure    vom F.

   215-216  und  anschliessende     Veresterung    mit     Pyridin-Pro-          pionsäureanhydrid)    schüttelt man     in    einer  Lösung von 250     Volumteilen    Wasser und ss       Gewichtsteilen        Natriumhydrogyd    mit 5 Ge  wichtsteilen eines Nickelkatalysators     unter          Wasserstoff.    Nach der Aufnahme der für  1     Moläquivalent    berechneten Menge Wasser  stoff wird vom Katalysator     abfiltriert    und  das Filtrat mit     Mineralsäure    angesäuert.

   Man  nimmt in Äther auf, trocknet die Äther  lösung     und    dampft ein. Durch     Umkristalli-          sieren    des Rückstandes aus einem     Aceton-          2lfethylalkohol-Gemisch    erhält man die     oestro-          gen    wirksame 1-Äthyl-2-methyl-7-propionyl       ogy-1,2,3,4-tetrahydro-phenanthren-2-carbon-          säure    der Formel  
EMI0001.0077     
    in Form farbloser     Kristalle.  



  Process for the preparation of a new oxydronhenanthrene derivative It has been found that a new ogyhydrophenanthrene derivative can be obtained if a 1-ethylidene-2-methyl-7-propionylogy-1,2,3,4-tetrahydro- phenanthrene-2-carboxylic acid 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, diel-ethyl-2-methyl-7-propionyl-1,2,3,4-tetrahydro-phenanthrene-2-carboxylic acid, shows up both on parenteral and on 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.

           Example: 6 parts by weight of 1-ethylidene-2-methyl-7-propionylogy-1,2, 3,4-tetrahydr o-phenanthrene-2-carboxylic acid of the formula
EMI0001.0035
    (receive e.g.

   from 1-keto-2-methyl-7-methoxy-1,2,3,4-tetrahydro-phenanthrene-2-carboxylic acid methyl ester by Grignardation with ethyl magnesium bromide, elimination of water from the 1-ethyl-1 thus obtained -ogy-2- methyl - 7 - methogy -1, 2,3,4 = tetrahydro-phen- anthrene - 2 - carboxylic acid - methyl ester from F.

   153, saponification with potassium hydrogen at 200 in the inclusion tube to 1-ethylidene-7-ogy - 2 - methyl -1,2,3,4 - tetrahydeo - phenanthrene-2-carboxylic acid from F.

   215-216 and subsequent esterification with pyridine-propionic anhydride) is shaken in a solution of 250 parts by volume of water and 3 parts by weight of sodium hydrogen 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-propionyl-1,2,3,4-tetrahydro-phenanthrene-2-carboxylic acid the formula
EMI0001.0077
    in the form of colorless crystals.

Claims (1)

PATENTANSPRUCH: Verfahren zur Herstellung eines neuen Oxyhydrophenanthren-Derivates, dadurch ge kennzeichnet, dass man eine 1-Äthyliden-2- methyl - 7 -propionyloxy-1,2,3,4 - tetrahydro- phenanthren-2-carbonsäure zwecks Überfüh rung der Athylidengruppierung in einen Äthylrest mit hydrierenden Mitteln behan delt. PATENT CLAIM: A process for the preparation of a new oxyhydrophenanthrene derivative, characterized in that a 1-ethylidene-2-methyl-7-propionyloxy-1,2,3,4-tetrahydro- phenanthrene-2-carboxylic acid is used for the purpose of transferring the ethylidene group treated in an ethyl residue with hydrogenating agents. Das noch nicht bekannte Endprodukt des Verfahrens, diel-Äthyl-2-methyl-7-propionyl 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. UNTERANSPRUCH: Verfahren gemäss Patentanspruch, da durch gekennzeichnet, dass man die Hydrie rung in Alkalilauge in Gegenwart eines Nickelkatalysators vornimmt. The as yet unknown end product of the process, diel-ethyl-2-methyl-7-propionyl oxy-1; 2,3,4-tetrahydro-phenanthrene-2-carboxylic acid; shows an extraordinarily high estrogenic effect both on parenteral and on oral administration. It should find therapeutic use or serve as an intermediate product for the preparation of therapeutically ver usable compounds. SUBCLAIM: Process according to claim, characterized in that the hydrogenation is carried out in alkali in the presence of a nickel catalyst.
CH250808D 1944-01-10 1944-01-10 Process for the preparation of a new oxyhydrophenanthrene derivative. CH250808A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH250808T 1944-01-10
CH242609T 1944-01-10

Publications (1)

Publication Number Publication Date
CH250808A true CH250808A (en) 1947-09-15

Family

ID=25728711

Family Applications (1)

Application Number Title Priority Date Filing Date
CH250808D CH250808A (en) 1944-01-10 1944-01-10 Process for the preparation of a new oxyhydrophenanthrene derivative.

Country Status (1)

Country Link
CH (1) CH250808A (en)

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