CH250807A - 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
CH250807A
CH250807A CH250807DA CH250807A CH 250807 A CH250807 A CH 250807A CH 250807D A CH250807D A CH 250807DA CH 250807 A CH250807 A CH 250807A
Authority
CH
Switzerland
Prior art keywords
methyl
tetrahydro
derivative
preparation
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 CH250807A publication Critical patent/CH250807A/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

  

      \C          Verfahren    zur Herstellung     eines    neuen     Oxyhydrophenanthren-Derivat%       Es     wurde    gefunden, dass man zu     einem     neuen     Oxyhydrophenanthren-Derivat    gelan  gen     kann,    wenn man eine.

       1-Athyliden-2-          methyl.-    7 -     acetoxy    -1, 2, 3,4 -     tetrahydro        -@        phen-          anthren-2-carbonsäure    zwecks     Überführung     der     Äthylidengruppierung        in        einen        Athylrest     mit hydrierenden Mitteln behandelt.  



       Für    die     Überführung    der     Athylidengrup-          pierung        in    den     Athylrest        kann        beispielsweise     die katalytische     Hydrierung    dienen.  



  Das noch nicht     bekannte    Endprodukt des  Verfahrens, die     1-Athyl-2-methyl-7-acetoxy-          1,2,3,4-tetrahydro-phenanthren-2-carbonsä.ure     vom F. 178-180 , zeigt sowohl bei par  enteraler als auch bei oraler Applikation eine  ausserordentlich hohe     oestrogene        Wirkung.     Es soll     therapeutische        Verwendung    finden  oder     als        Zwischenprodukt    zur     Herstellung          therapeutisch    verwendbarer     Verbindungen     dienen.  



  <I>Beispiel:</I>  6     Gewichtsteile        1-Äthyliden-2-methyl-7-          aeetoxy    -1,2,3,4 -     tetrahydro    -     phenanthren-        2-          carbonsäure    der     Formel            säure-methylester    durch     Grignardierung    mit       Äthya-magneGiumbromid,        Wasserabspaltung          aus    dem so erhaltenen     1-Athyl-l-oxy-2-          methyl        -4    7     -methc,xy-1,2,3,

  4-tetrahydro-phen-          anthren    - 2 -     carbonsäure    -     methylester    vom  F. 153 ,     Verseifung    mit     galiumhydroxyd     bei 200  im     Einschlussrohr    zur     1-Athyliden-          7    -     oxy    - 2 -     methyl    -1,2,3,4 -     tetrahydro    -     phen-          anthren-2-carbonsäure    vom F.

   215-216  und  anschliessende     Veresterung    mit     Pyridin-Acet-          anhydrid)    schüttelt man in einer Lösung von  250     Volumteilen    Wasser und 8 Gewichts  teilen     Natriumhydroxyd    mit 5     Gewichts-          teilen    eines     Nickelkatalysators    unter Wasser  stoff.

   Nach der Aufnahme der für 1     Mol-          äquivalent        berechneten    Menge     Wasserstoff     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-          Methylalkohol-Gemisch    erhält man die     oestro-          gen        wirksame        1-Athyl-2-methyl-7-acetoxy-          1,2,3,4-tetrahydro-phenanthren-2-carbonsäure     der Formel  
EMI0001.0103     
    (erhalten z.

   B.     aus    1-Keto-2-methyl-7-meth  oxy-1,2,3,4-tetrahydro-phenanthren-2-carbon-    in Form farbloser     Kristalle    vom F. 178 bis  180 .



      \ C Process for the preparation of a new oxyhydrophenanthrene derivative% It has been found that a new oxyhydrophenanthrene derivative can be obtained if one.

       1-Ethyliden-2- methyl.- 7 - acetoxy -1, 2, 3,4 - tetrahydro - @ phen- anthrene-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, the 1-ethyl-2-methyl-7-acetoxy-1,2,3,4-tetrahydro-phenanthrene-2-carboxylic acid from F. 178-180, shows both in par enteraler as well as an extremely high estrogenic effect when administered orally. It should find therapeutic use or serve as an intermediate for the preparation of therapeutically useful compounds.



  <I> Example: </I> 6 parts by weight of 1-ethylidene-2-methyl-7-aeetoxy -1,2,3,4-tetrahydro-phenanthrene-2-carboxylic acid of the formula acid methyl ester by Grignarding with ethya magnesium bromide, Elimination of water from the 1-ethyl-l-oxy-2-methyl -4 7 -methc, xy-1,2,3,

  4-tetrahydro-phen- anthrene - 2 - carboxylic acid - methyl ester of F. 153, saponification with galium hydroxide at 200 in the inclusion tube to 1-ethylidene- 7 - oxy - 2 - methyl -1,2,3,4 - tetrahydro - phen- anthrene-2-carboxylic acid from F.

   215-216 and subsequent esterification with pyridine acetic anhydride) is shaken under hydrogen 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.

   After the amount of hydrogen calculated for 1 mol equivalent has been taken up, the catalyst is filtered off and the filtrate is acidified with mineral acid. One absorbs into ether

   the ether solution dries and evaporates. Recrystallization of the residue from an acetone-methyl alcohol mixture gives the estrogenically active 1-ethyl-2-methyl-7-acetoxy-1,2,3,4-tetrahydrophenanthrene-2-carboxylic acid of the formula
EMI0001.0103
    (received e.g.

   B. from 1-keto-2-methyl-7-methoxy-1,2,3,4-tetrahydro-phenanthrene-2-carbon- in the form of colorless crystals with a melting point of 178 to 180.

Claims (1)

PATUNTANAPUÜOH: Verfahren zur Herstellung eines neuen Ogyhydrophenanthren-Derivates, dadurch ge kennzeichnet, dass man eine 1-Äthyliden-2- methyl - 7 -:acetogy-1,2,3,4-,tetrahydro-phen- anthren.-2-oarbonsäure zwecks Überführung der Äthylidengruppierung in einen Äthylrest mit hydrierenden Mitteln behandelt. PATUNTANAPUÜOH: Process for the production of a new Ogyhydrophenanthren derivative, characterized in that one 1-ethylidene-2-methyl-7 -: acetogy-1,2,3,4-, tetrahydro-phen-anthrene-2-oarboxylic acid treated with hydrogenating agents for the purpose of converting the ethylidene group into an ethyl radical. Das noch nicht bekannte Endprodukt des Verfahrens, die 1-Äthyl-2-methyl-7-acetosy- 1,2,3,4-tetrahydro-phenanthren- 2-carbonsäure vom F. 178-180 , zeigt sowohl bei par- enteraler als auch bei oraler Applikation eine ausserordentlich hohe oestrogene Wirkung. Es soll therapeutische Verwendung finden oder als Zwischenprodukt zur Herstellung therapeutisch verwendbarer Verbindungen dienen. The as yet unknown end product of the process, the 1-ethyl-2-methyl-7-acetosy-1,2,3,4-tetrahydro-phenanthrene-2-carboxylic acid of F. 178-180, shows both parenteral and an extraordinarily high estrogenic effect even with oral administration. It should find therapeutic use or serve as an intermediate for the preparation of therapeutically useful compounds. UNTERANBPRÜCH: Verfahren gemäss Patentanspruch, da durch gekennzeichnet, dass man die Hydrie rung in Alkalilauge in Gegenwart eines Nickelkatalysators vornimmt. SUBSTANTIAL CLAIM: Process according to claim, characterized in that the hydrogenation is carried out in alkali in the presence of a nickel catalyst.
CH250807D 1944-01-10 1944-01-10 Process for the preparation of a new oxyhydrophenanthrene derivative. CH250807A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH242609T 1944-01-10
CH250807T 1944-01-10

Publications (1)

Publication Number Publication Date
CH250807A true CH250807A (en) 1947-09-15

Family

ID=25728710

Family Applications (1)

Application Number Title Priority Date Filing Date
CH250807D CH250807A (en) 1944-01-10 1944-01-10 Process for the preparation of a new oxyhydrophenanthrene derivative.

Country Status (1)

Country Link
CH (1) CH250807A (en)

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