CH245882A - Process for the preparation of a new oxyhydrophenanthrene derivative. - Google Patents

Process for the preparation of a new oxyhydrophenanthrene derivative.

Info

Publication number
CH245882A
CH245882A CH245882DA CH245882A CH 245882 A CH245882 A CH 245882A CH 245882D A CH245882D A CH 245882DA CH 245882 A CH245882 A CH 245882A
Authority
CH
Switzerland
Prior art keywords
preparation
derivative
ethyl
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 CH245882A publication Critical patent/CH245882A/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     znr    Herstellung eines neuen     Oxyhydrophenanthren-Derivates.       Es wurde gefunden, dass man zu     einem     neuen     Ogyhydrophenanthren-Derivat    gelan  gen kann, wenn man eine     1-Methyliden-2-          äthyl    - 7 -     methogy    -     1,2,'0,

  4    -     tetrahydrophen-          anthren-2-carbonsäure    zwecks Überführung  der     Methylidengruppierung    in     einen        Methyl-          rest    mit hydrierenden     Mitteln    behandelt.  



  Für die Überführung der     Methyliden-          gruppierung    in den     Methylrest    kann bei  spielsweise die katalytische Hydrierung       dienen.     



  Das noch nicht bekannte Endprodukt des  Verfahrens, die     1-Methyl-2-äthyl-7-methoxy-          1,2,3,4-tetrahydrophenanthren-2-carbonsäure     vom F. 178-174 , zeigt sowohl bei     par-          enteraler    als auch bei oraler Applikation  eine ausserordentlich hohe     östrogene    Wir  kung. Es soll therapeutische Verwendung  finden oder als Zwischenprodukt zur Her  stellung therapeutisch verwendbarer Verbin  dungen dienen.  



  <I>Beispiel:</I>  6 Gewichtsteile     1-Methyliden-2-äthyl-7-          methogy    - 1,2,3,4 -     tetrahydrophenanthren    -     2-          carbonsäure    vom F. 178-179  der     Formel     
EMI0001.0031     
    (erhalten z.

       B.    aus 1-Keto-2-äthyl-7-methogy       1,2,3,4-tetrahydrophenanthren-2-carbonsäure-          methylester    durch     Grignardierung    mit     Me-          thyl    -     magnesiumbromid,    Wasserabspaltung  aus dem so erhaltenen     1-Methyl-l-ogy-2-          äthyl    - 7 -     methogy    - 1,2,8,4 -     tetrahydrophen-          anthren-2-carbonsäure-methylester    und an  schliessende     Verseifung    mit     Kaliumhydroayd     bei l60 )

   schüttelt man bei 50  in einer Lö  sung von 250     Volumteilen    Wasser und 8 Ge  wichtsteilen     Natriumhydrogyd    mit 5     Ge-          a@ichtsteilen    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     UmkristaIli-          sieren    des     Rückstandes    aus verdünntem      Methanol und     Aceton-Petroläther-Gemisch     erhält man die     östrogen    wirksame     1-Methyl-          2    -     äthyl    -7     -methogy-1,2,3,4        -tetrahydrophen-          anthren-2-carbonsäure    der     Formel     
EMI0002.0010     
    in Form farbloser     Kristalle    vom F. 173  bis 174 .



  Process for the preparation of a new oxyhydrophenanthrene derivative. It has been found that a new ogyhydrophenanthrene derivative can be obtained if a 1-methylidene-2-ethyl-7-methogy-1,2, '0,

  4 - tetrahydrophen- anthrene-2-carboxylic acid treated with hydrogenating agents for the purpose of converting the methylidene grouping into a methyl radical.



  Catalytic hydrogenation, for example, can be used to convert the methylidene group into the methyl radical.



  The as yet unknown end product of the process, the 1-methyl-2-ethyl-7-methoxy-1,2,3,4-tetrahydrophenanthrene-2-carboxylic acid of F. 178-174, shows both in parenteral and in oral application has an extraordinarily high estrogenic effect. It should be used therapeutically or serve as an intermediate for the preparation of therapeutically usable compounds.



  <I> Example: </I> 6 parts by weight of 1-methylidene-2-ethyl-7-methogy - 1,2,3,4 - tetrahydrophenanthrene - 2-carboxylic acid with a melting point of 178-179 of the formula
EMI0001.0031
    (received e.g.

       B. from 1-keto-2-ethyl-7-methogy 1,2,3,4-tetrahydrophenanthrene-2-carboxylic acid methyl ester by Grignardation with methyl - magnesium bromide, elimination of water from the 1-methyl-1-ogy thus obtained -2- ethyl - 7 - methogy - 1,2,8,4 - tetrahydrophen- anthrene-2-carboxylic acid methyl ester and subsequent saponification with potassium hydroxide at 160)

   it 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 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.

   By recrystallizing the residue from dilute methanol and acetone-petroleum ether mixture, the estrogenically active 1-methyl-2-ethyl-7-methoxy-1,2,3,4-tetrahydrophenanthene-2-carboxylic acid of the formula is obtained
EMI0002.0010
    in the form of colorless crystals from F. 173 to 174.

Claims (1)

PATENTANSPRUCH: Verfahren zur Herstellung eines neuen Ogyhydrophenanthren-Derivates, dadurch ge kennzeichnet, dass man eine 1-Methyliden-2- äthyl - 7 - methogy -1,2,3,4 - tetrahydrophen- anthren-2-carbonsäure zwecks Überführung der Methylidengruppierung in einen Methyl- rest mit hydrierenden Mitteln behandelt. PATENT CLAIM: Process for the preparation of a new Ogyhydrophenanthren derivative, characterized in that one 1-methylidene-2-ethyl - 7 - methogy -1,2,3,4 - tetrahydrophen- anthrene-2-carboxylic acid for the purpose of converting the methylidene group into treated a methyl residue with hydrogenating agents. Das noch nicht bekannte Endprodukt des Verfahrens, die 1-Methyl-2-äthyl-7-methogy- 1, 2, 3,4 - tetrahydrophenanthren-2- carbonsäure vom F. 173--174 , zeigt sowohl bei par- enteraler als auch bei oraler Applikation eine ausserordentlich hohe östrogene Wir- kung. Es soll therapeutische Verwendung finden oder als Zwischenprodukt zur Her stellung therapeutisch verwendbarer Verbin dungen dienen. UNTERANSPRÜCHE; -1. The as yet unknown end product of the process, 1-methyl-2-ethyl-7-methogy-1, 2, 3,4-tetrahydrophenanthrene-2-carboxylic acid of F. 173-174, shows both parenteral and an extremely high estrogenic effect when administered orally. It should be used therapeutically or serve as an intermediate for the preparation of therapeutically usable compounds. SUBCLAIMS; -1. Verfahren gemäss Patentanspruch, da durch gekennzeichnet, dass man ein Salz der genannten Säure hydriert. 2. Verfahren gemäss Patentanspruch, da durch gekennzeichnet, dass man die Hydrie rung in Alkalilauge in Gegenwart eines Nickelkatalysators vornimmt. Process according to patent claim, characterized in that a salt of said acid is hydrogenated. 2. The method according to claim, characterized in that the hydrogenation is carried out in alkali in the presence of a nickel catalyst.
CH245882D 1944-01-10 1944-01-10 Process for the preparation of a new oxyhydrophenanthrene derivative. CH245882A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH242609T 1944-01-10
CH245882T 1944-01-10

Publications (1)

Publication Number Publication Date
CH245882A true CH245882A (en) 1946-11-30

Family

ID=25728706

Family Applications (1)

Application Number Title Priority Date Filing Date
CH245882D CH245882A (en) 1944-01-10 1944-01-10 Process for the preparation of a new oxyhydrophenanthrene derivative.

Country Status (1)

Country Link
CH (1) CH245882A (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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