CH245879A - Process for the preparation of a new oxyhydrophenanthrene derivative. - Google Patents

Process for the preparation of a new oxyhydrophenanthrene derivative.

Info

Publication number
CH245879A
CH245879A CH245879DA CH245879A CH 245879 A CH245879 A CH 245879A CH 245879D A CH245879D A CH 245879DA CH 245879 A CH245879 A CH 245879A
Authority
CH
Switzerland
Prior art keywords
preparation
new
derivative
oxyhydrophenanthrene
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 CH245879A publication Critical patent/CH245879A/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
    • 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
    • C07C62/34—Unsaturated compounds containing ether groups, groups, groups, or groups
    • 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     Ogyhydrophenanthren-Derivates.       Es wurde gefunden, dass man zu einem  neuen     Oxyhydrophenanthren-Derivat    gelangen  kann, wenn man eine     1-Methyliden-2-methyl-          7        -methoxy        -1,2,3,4-tetrahydrophenanthren    - 2     -          carbonsänre    zwecks Überführung der     Methyl-          idengruppierung    in einen     Methylrest    mit hy  drierenden     Mitteln    behandelt.  



  Für die Überführung der     Methyliden-          gruppierung    in den     Methylrest    kann beispiels  weise die     katalytische    Hydrierung dienen.    Das neue Verfahrensprodukt, die     östrogen     wirksame 1,2 -     Dimethyl    -     7-methoxy    -1,2,3,4     -          tetrahydrophenanthren    - 2 -     carbonsäure    vom  F. 228  , soll therapeutische Verwendung     finden     oder als Zwischenprodukt zur Herstellung the  rapeutisch verwendbarer Verbindungen dienen.

    <I>Beispiel:</I>  3 Gewichtsteile 1-Methyliden -2-methyl-7       methoxy-1,2,3,4-tetrahydrophenanthren-2-car-          bonsäure    vom F. 189   der Formel  
EMI0001.0026     
    (erhalten z. B. aus     1-geto-2-methyl-7-methoxy-          1,2,3,4    -     tetrahydr        ophenanthr    en-     2-carbonsäure-          methylester    durch     Grignardierung    mit     Methyl-          magnesiumbromid,    Wasserabspaltung aus dem  so erhaltenen 1,2-Dimethyl-l-oxy-7-methoxy       1,2,3,

  4-tetrahydrophenanthren-2-carbonsäure-          methylester    vom F.     135-13611    und anschlie-         ssende        Verseifung    mit     galiumhydroxyd    bei  160  ) werden bei 50   in einer Mischung von  8     GewichtsteilenNatriumhydroxyd,    250     Volum-          teilen    Wasser und 3 Gewichtsteilen eines       Nickelkatalysators    unter     Wasserstoff    geschüt  telt.

   Nach der Aufnahme der für     1,1-112oläqui-          valente    berechneten Menge     Wasserstoff    bleibt      die Hydrierung stehen. Das ausgefallene       schwerlösliche        Natriumsalz    bringt man durch  Erwärmen in Lösung, worauf der Katalysator       abfiltriert    und das Filtrat mit Salzsäure ange  säuert wird.

   Das ausgefallene Produkt führt    durch     Umkristallisieren    aus verdünntem     Me-          tbylall.:ohol    zur     östrogen    wirksamen     1,2-          Dimethyl    -     7-methoxy-1,2,3,4-tetrahydrophen-          anthren-2-carbongäure    der Formel  
EMI0002.0012     
    vom F.<B>2280</B> nebst einer geringen Menge  eines unwirksamen     Diastereoisomeren    vom  F. 183 -185  .



  Process for the preparation of a new ogyhydrophenanthrene derivative. It has been found that a new oxyhydrophenanthrene derivative can be obtained if a 1-methylidene-2-methyl-7-methoxy -1,2,3,4-tetrahydrophenanthrene-2-carboxylic acid is used to convert the methylidene group into treated a methyl radical with hy drating agents.



  Catalytic hydrogenation, for example, can be used to convert the methylidene group into the methyl radical. The new process product, the estrogenic 1,2 - dimethyl - 7-methoxy -1,2,3,4 - tetrahydrophenanthrene - 2 - carboxylic acid from F. 228, is intended to be used therapeutically or as an intermediate for the preparation of compounds which can be used therapeutically.

    <I> Example: </I> 3 parts by weight of 1-methylidene -2-methyl-7-methoxy-1,2,3,4-tetrahydrophenanthrene-2-carboxylic acid with a melting point of 189 of the formula
EMI0001.0026
    (obtained e.g. from 1-geto-2-methyl-7-methoxy-1,2,3,4-tetrahydrophenanthrene-2-carboxylic acid methyl ester by Grignardation with methyl magnesium bromide, elimination of water from the 1 obtained in this way, 2-dimethyl-1-oxy-7-methoxy 1,2,3,

  4-tetrahydrophenanthrene-2-carboxylic acid methyl ester of F. 135-13611 and subsequent saponification with galium hydroxide at 160) are shaken under hydrogen at 50 in a mixture of 8 parts by weight of sodium hydroxide, 250 parts by volume of water and 3 parts by weight of a nickel catalyst.

   The hydrogenation stops after the amount of hydrogen calculated for 1.1-112ol equivalents has been absorbed. The precipitated sparingly soluble sodium salt is brought into solution by heating, whereupon the catalyst is filtered off and the filtrate is acidified with hydrochloric acid.

   The precipitated product leads by recrystallization from dilute methylall.:ohol to the estrogenically active 1,2-dimethyl-7-methoxy-1,2,3,4-tetrahydrophenanthene-2-carbonic acid of the formula
EMI0002.0012
    from F. <B> 2280 </B> together with a small amount of an inactive diastereoisomer from F. 183-185.

Claims (1)

PATENTANSPRUCH: Verfahren zur Herstellung eines neuen Oxyhydrophenanthren-Derivates, dadurch ge kennzeichnet, dass man eine 1-Methyliden-2- methyl- 7 -methoxy - 1,2,3,4 - tetrahydropheii- anthren-2-carbonsäure zwecks Überführung der Methylidengruppierung in einen Methyl- rest mit hydrierenden Mitteln behandelt. PATENT CLAIM: A process for the preparation of a new oxyhydrophenanthrene derivative, characterized in that a 1-methylidene-2-methyl-7-methoxy-1,2,3,4-tetrahydropheii- anthrene-2-carboxylic acid for the purpose of converting the methylidene group into treated a methyl residue with hydrogenating agents. Das neue Verfahrensprodukt, die östrogen wirksame 1,2 - Dimethyl- 7 -methoxy -1,2,3,4 tetrahydrophenanthren - 2 - carbonsäure vom F. 228 , soll therapeutische Verwendung finden oder als Zwischenprodukt zur Herstellung therapeutisch verwendbarer Verbindungen dienen. UN TERANSPRüCHE 1. Verfahren gemäss Patentanspruch, da durch gekennzeichnet, dass man ein Salz der genannten Säure hydriert. 2. The new process product, the estrogenic 1,2-dimethyl-7-methoxy -1,2,3,4 tetrahydrophenanthrene-2-carboxylic acid of F. 228, is intended to be used in therapy or as an intermediate for the preparation of therapeutically useful compounds. UN TERCLAIMS 1. Process according to patent claim, characterized in that a salt of said acid is hydrogenated. 2. Verfahren gemäss Patentanspruch, da durch gekennzeichnet, dass man die Hydrierung in Alkalilauge in Gegenwart eines Nickel- katalysators vornimmt. Process according to patent claim, characterized in that the hydrogenation is carried out in alkali in the presence of a nickel catalyst.
CH245879D 1944-01-10 1944-01-10 Process for the preparation of a new oxyhydrophenanthrene derivative. CH245879A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH242609T 1944-01-10
CH245879T 1944-01-10

Publications (1)

Publication Number Publication Date
CH245879A true CH245879A (en) 1946-11-30

Family

ID=25728703

Family Applications (1)

Application Number Title Priority Date Filing Date
CH245879D CH245879A (en) 1944-01-10 1944-01-10 Process for the preparation of a new oxyhydrophenanthrene derivative.

Country Status (1)

Country Link
CH (1) CH245879A (en)

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