CH242609A - Process for the preparation of a new oxyhydrophenanthrene derivative. - Google Patents

Process for the preparation of a new oxyhydrophenanthrene derivative.

Info

Publication number
CH242609A
CH242609A CH242609DA CH242609A CH 242609 A CH242609 A CH 242609A CH 242609D A CH242609D A CH 242609DA CH 242609 A CH242609 A CH 242609A
Authority
CH
Switzerland
Prior art keywords
preparation
methyl
derivative
new
carboxylic acid
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 CH242609A publication Critical patent/CH242609A/en

Links

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

Landscapes

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

Description

  

  Verfahren zur Herstellung eines neuen     Ogyhydrophenanthren-Derlvates.       Es     wurde    gefunden, dass man zu einem  neuen     Ogyhydrophenanthren-Derivat    gelan  gen     kann,    wenn man     eine        1-Äthyliden-2-          methyl    - 7 -     methogy-1,2,3,4    -     tetrahydrophen-          anthren-2-carbonsäure    zwecks     Überführung     der     Äthylidengruppierung        in    einen     Äthylrest     mit hydrierenden Mitteln behandelt.  



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



  Das noch nicht     bekannte    Endprodukt des  Verfahrens, die     1-Äthyl-2-methyl-7-methogy-          1,2,3,4-tetrahydrophenanthren-2-carbonsäure     vom F.228-230 , zeigt sowohl bei     paren-          teraler    als auch bei oraler Applikation eine       ausserordentlich    hohe     östrogene    Wirkung. Es  soll therapeutische Verwendung finden oder  als Zwischenprodukt zur     Herstellung    thera  peutisch verwendbarer Verbindungen dienen.

    <I>Beispiel:</I>  6     Gewichtsteile        1-Äthyliden-2-methyl-7-          methogy    -1,2;3,4 -     tetrahydrophenanthren    - 2     -          carbonsäure    vom F. 213 bis 215  der Formel.  
EMI0001.0032     
    (erhalten z.

   B. aus     1-geto-2-methyl-7-me-          thogy    -1,2,3,4-     tetrahydrophenanthren-    2 -     car-          bonsäure-methylester    durch     Grignardierung     mit     Äthyl-magnesiumbromid,    Wasserabspal  tung aus dem so erhaltenen     1-Äthyl-l-ogy-2-          methyl    - 7 -     methogy-1,2,3,4-tetrahydrophen-          anthren-2-carbonsäure-methylestervomF.153      und anschliessende     Verseifuug    mit     Kalium-          hydrogyd    bei 160 )

   schüttelt man bei 50        in.    einer     Lösung    von 250     Volumenteilen    Was  ser und 8 Gewichtsteilen     Natriumhydrogyd     mit 5     Gewichtsteilen        eines    Nickelkatalysators       unter    Wasserstoff. Nach der     Aufnahme    der  für 1     Moläquivalent    entsprechenden 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-Me-          thylalkohol-Gemisch    erhält man die     östrogen-          wirksame        1-Äthyl    - 2 -     methyl    - 7 -     methogy-          1,2,3,4-tetrahydrophenanthren-2        -carbonsäure     der Formel  
EMI0002.0016     
    in Form farbloser Kristalle vom F.

   228 bis  230' nebst     einer        geringen.    Menge     eines    un  wirksamen     -Diastereoisomeren    vom F, 204 bis  200'.



  Process for the production of a new ogyhydrophenanthrene derivative. It has been found that a new ogyhydrophenanthrene derivative can be obtained if a 1-ethylidene-2-methyl-7-methogy-1,2,3,4-tetrahydrophen-anthrene-2-carboxylic acid is used to convert the ethylidene group treated into an ethyl residue with hydrogenating agents.



  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-methogy-1,2,3,4-tetrahydrophenanthrene-2-carboxylic acid from F.228-230, shows both parenteral and oral application has an extraordinarily high estrogenic effect. 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-methogy -1,2; 3,4 - tetrahydrophenanthrene - 2 - carboxylic acid with a melting point of 213 to 215 of the formula.
EMI0001.0032
    (received e.g.

   B. from 1-geto-2-methyl-7-methogy -1,2,3,4-tetrahydrophenanthrene- 2 - carboxylic acid methyl ester by Grignardation with ethyl magnesium bromide, elimination of water from the 1-ethyl thus obtained -l-ogy-2- methyl - 7 - methogy-1,2,3,4-tetrahydrophen- anthrene-2-carboxylic acid methyl ester from F.153 and subsequent saponification with potassium hydrogyd at 160)

   is shaken at 50 in. A solution of 250 parts by volume of water and 8 parts by weight of sodium hydrogen with 5 parts by weight of a nickel catalyst under hydrogen. After the amount of hydrogen corresponding to 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 estrogen-active 1-ethyl-2-methyl-7-methogy-1,2,3,4-tetrahydrophenanthrene-2-carboxylic acid of the formula
EMI0002.0016
    in the form of colorless crystals from F.

   228 to 230 'plus a small one. Amount of an ineffective -diastereoisomer of F, 204 to 200 '.

Claims (1)

PATENTANSPRUCH: Verfahren zur Herstellung eines neuen Oxyhydrophenanthren-Derivates, dadurch ge kennzeichnet, dass man eine 1-Äthyliden-2- methyl - 7 \methogy -1,2,3,4 - tetrahydrophen- anthren-2-carbonsäure zwecks Überführung der Äthylidengruppierung in einen Äthylrest mit hydrierenden Mitteln behandelt. PATENT CLAIM: Process for the preparation of a new Oxyhydrophenanthren derivative, characterized in that a 1-ethylidene-2-methyl - 7 \ methogy -1,2,3,4 - tetrahydrophen- anthrene-2-carboxylic acid for the purpose of converting the ethylidene group into treated an ethyl residue with hydrogenating agents. Das noch nicht bekannte Endprodukt des Verfahrens, die l-Äthyl-2-methyl-7-methoay- 1, 2, 3,4-tetrahydrophenanthren- 2 - carbonsäure vom F. 228 bis 230', The not yet known end product of the process, the l-ethyl-2-methyl-7-methoay- 1, 2, 3,4-tetrahydrophenanthrene-2-carboxylic acid from F. 228 to 230 ', zeigt sowohl bei paren- teraler als auch bei oraler -Applikation eine ausserordentlich hohe östrogene Wirkung. Es soll therapeutische Verwendung finden oder als Zwischenprodukt zur Herstellung thera peutisch verwendbarer Verbindungen dienen. UNTERAIVTSPRÜCHE 1. Verfahren gemäss Patentanspruch, da durch gekennzeichnet, dass man ein Salz der genannten Säure hydriert. 2. shows an extraordinarily high estrogenic effect with both parenteral and oral application. It should find therapeutic use or serve as an intermediate for the preparation of therapeutically useful compounds. UNTERAIVTSPRÜCHE 1. A method according to claim, characterized in that a salt of said acid is hydrogenated. 2. Verfahren gemäss Patentanspruch, da durch gekennzeichnet, dass man die Hydrie rung in Alkalilauge in Gegenwart eines Nik- kelkatalysators vornimmt. Process according to patent claim, characterized in that the hydrogenation is carried out in alkali in the presence of a nickel catalyst.
CH242609D 1944-01-10 1944-01-10 Process for the preparation of a new oxyhydrophenanthrene derivative. CH242609A (en)

Applications Claiming Priority (1)

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

Publications (1)

Publication Number Publication Date
CH242609A true CH242609A (en) 1946-05-31

Family

ID=4463052

Family Applications (1)

Application Number Title Priority Date Filing Date
CH242609D CH242609A (en) 1944-01-10 1944-01-10 Process for the preparation of a new oxyhydrophenanthrene derivative.

Country Status (1)

Country Link
CH (1) CH242609A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1049855B (en) * 1959-02-05 CIBA Aktiengesellschaft, Base' (Schweiz) Process for the preparation of methylenehydrophenanthrenes

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1049855B (en) * 1959-02-05 CIBA Aktiengesellschaft, Base' (Schweiz) Process for the preparation of methylenehydrophenanthrenes

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