CH250806A - Process for the preparation of a new oxyhydrophenanthrene derivative. - Google Patents

Process for the preparation of a new oxyhydrophenanthrene derivative.

Info

Publication number
CH250806A
CH250806A CH250806DA CH250806A CH 250806 A CH250806 A CH 250806A CH 250806D A CH250806D A CH 250806DA CH 250806 A CH250806 A CH 250806A
Authority
CH
Switzerland
Prior art keywords
methyl
phenanthrene
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 CH250806A publication Critical patent/CH250806A/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     Oxyhydrophenanthren-Derivates.       Es     wurde        gefunden,    dass man zu einem  neuen     Ogyhydroj?henanthren-Derivat    gelan  gen kann, wenn man eine     1-Äthyliden-2-          methyl-    7 -     methogy-1,2,3,4,9,

  10    -     hexahydro-          phenanthren-2-carbonsäure    zwecks     Überfüh-          rung    der     Äthylidengruppierung    in einen       Athylrest    mit hydrierenden     Mitteln    be  handelt.  



  Für die     Überführung    der     Äthyliden-          gruppierung    in den     Äthylrest    kann     beispiels-          weise    die     katalytische        Hydrierung    dienen.  



  Das noch nicht bekannte Endprodukt des  Verfahrens, die     1-Äthyl-2-methyl-7-meth-          oxy-1,2,3,4,9,10        -hexahydro-phenanthren-        2-          earbonsäure    vom F.

   168-170 , zeigt sowohl  bei     parenteraler    als auch bei oraler     Applika-          tion        eine    ausserordentlich hohe     oestrogene          Wirkung.    Es soll     therapeutische    Verwen  dung     finden    oder als     Zwischenprodukt    zur  Herstellung therapeutisch     verwendbarer    Ver  bindungen dienen.  



  <I>Beispiel:</I>  3     Gewichtsteile    1-Äthyliden-2-methyl-7       methoxy-1,2,3,4,9,10-hexahydro-phenanthren-          2-carbonsäure    vom F.     191--193     der     Formel     
EMI0001.0044     
    (erhalten z.

   B. aus     1-geto-2-methyl-7-meth-          oxy        -1.,    2., 3,.4,     9,10@-;he$ahydro-phenanthren-          2-carbonsäure-methylester    durch     Grignardie-          rung        mit        Äthyl-magnesiumjodid,    Isolierung  des so erhaltenen 1-Äthyliden-2-methyl-7       methoxy-1,2,3,4,9,10-hexahydro-phenanthren-          2-carbonsäure-methylesber    vom F.

   146-147   und     anschliessende        Verseifung    mit     Kalium-          hydrogyd    bei 160 )     schüttelt    man bei 50  in  einer Lösung von 125     Volumteilen    Wasser  und 4     Gewichtsteilen        Natriumhydrogyd    mit  2,5     Gewichtsteilen    eines Nickelkatalysators  unter Wasserstoff. Nach der Aufnahme der  für 1     Moläquivalent        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     Umkrietalli-          sieren    des Rückstandes aus einem     Aceton-          Methylalkohol-Gemisch    erhält man die     oestro-          gen    wirksame 1-Äthyl-2-methyl-7-methoxy       1,2,3,4,9,10-hegahydro-phenanthren-2-carbon-          säure    der Formel  
EMI0001.0079     
         in.    Form farbloser     Kristalle    vom F.

   168     bis     170  nebst einer     geringen    Menge eines un  wirksamen     Diastereisomeren    vom F. 171 bis       173 .  



  Process for the preparation of a new oxyhydrophenanthrene derivative. It has been found that a new ogyhydrojhenanthrene derivative can be obtained if a 1-ethylidene-2-methyl-7-methogy-1,2,3,4,9,

  10 - hexahydro- 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, the 1-ethyl-2-methyl-7-methoxy-1,2,3,4,9,10-hexahydro-phenanthrene-2-carboxylic acid from F.

   168-170, shows an extraordinarily high estrogenic effect both on parenteral and on oral administration. It should find therapeutic use or serve as an intermediate for the preparation of therapeutically usable compounds.



  <I> Example: </I> 3 parts by weight of 1-ethylidene-2-methyl-7-methoxy-1,2,3,4,9,10-hexahydro-phenanthrene-2-carboxylic acid with a melting point of 191-193 of the formula
EMI0001.0044
    (received e.g.

   B. from 1-geto-2-methyl-7-methoxy -1., 2., 3, .4, 9,10 @ -; he $ ahydro-phenanthrene-2-carboxylic acid methyl ester by Grignardation with Ethyl magnesium iodide, isolation of the 1-ethylidene-2-methyl-7-methoxy-1,2,3,4,9,10-hexahydro-phenanthrene-2-carboxylic acid methyl acid obtained in this way from F.

   146-147 and subsequent saponification with potassium hydrogen at 160) is shaken at 50 in a solution of 125 parts by volume of water and 4 parts by weight of sodium hydrogen with 2.5 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. The estrogenically active 1-ethyl-2-methyl-7-methoxy 1,2,3,4,9,10-hegahydro-phenanthrene-2-carbon is obtained by recrystallizing the residue from an acetone-methyl alcohol mixture - acid of the formula
EMI0001.0079
         in the form of colorless crystals from F.

   168 to 170 together with a small amount of an ineffective diastereoisomer of F. 171 to 173.

Claims (1)

PATENTANSPRUCH: Verfahren zur Herstellung eines neuen Ogylhydrophenanthren-Derivates, dadurch ge- kennzeichnet, dass man eine 1-Äthyliden-2- methyl - 7 - methogy -1,2,3,4,9,10 -hegahydro- phenanthren-2-carbonsäure zwecks Überfüh rung der Äthylidengruppierung meinen Äthylrest mit hydrierenden Mitteln be handelt. PATENT CLAIM: Process for the production of a new Ogylhydrophenanthren derivative, characterized in that a 1-ethylidene-2-methyl-7-methogy -1,2,3,4,9,10 -hegahydro- phenanthrene-2-carboxylic acid for the purpose of transferring the ethylidene group, treating my ethyl residue with hydrogenating agents. Das noch nicht bekannte Endprodukt des Verfahrens, die 1-Ätbyl-2-methyl-7-meth- ogy -1, 2, 3,4, 9,10 - hegahydro - phenanthren - 2 carbonsäure vom F. 168-170 , zeigt sowohl bei parenteraler als auch bei oraler Applika tion eine ausserordentlich hohe oestrogene Wirkung. The as yet unknown end product of the process, the 1-ethyl-2-methyl-7-meth- ogy -1, 2, 3,4, 9,10 - hegahydro - phenanthrene - 2 carboxylic acid of F. 168-170, shows both an extraordinarily high estrogenic effect in both parenteral and oral application. Es soll therapeutische Verwen dung finden oder als Zwischenprodukt zur Herstellung therapeutisch verwendbarer Ver- bindungen dienen. UNTERANSPRUCH: Verfahren gemäss Patentanspruch, da durch .gekennzeichnet, dass man die Hydrie rung in Alkalilauge in Gegenwart eines Nickelkatalysators vornimmt. It should find therapeutic use or serve as an intermediate product for the production of therapeutically usable compounds. SUBClaim: Process according to claim, characterized by the fact that the hydrogenation is carried out in alkali in the presence of a nickel catalyst.
CH250806D 1944-01-10 1944-01-10 Process for the preparation of a new oxyhydrophenanthrene derivative. CH250806A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH242609T 1944-01-10
CH250806T 1944-01-10

Publications (1)

Publication Number Publication Date
CH250806A true CH250806A (en) 1947-09-15

Family

ID=25728709

Family Applications (1)

Application Number Title Priority Date Filing Date
CH250806D CH250806A (en) 1944-01-10 1944-01-10 Process for the preparation of a new oxyhydrophenanthrene derivative.

Country Status (1)

Country Link
CH (1) CH250806A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2621210A (en) * 1944-01-10 1952-12-09 Ciba Pharm Prod Inc Hexahydrophenanthrene carboxylic acids
US2687426A (en) * 1947-06-21 1954-08-24 Upjohn Co Process for the manufacture of a 1, 2-di-lower alkyl-2-carboxy-7 etherified hydroxy-1, 2, 3, 4, 9, 10-hexahydrophenanthrene
US2732389A (en) * 1956-01-24 I-methyl-z-carboxy-y-oxy derivatives of
FR2081337A1 (en) * 1969-12-09 1971-12-03 Syntex Corp

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2732389A (en) * 1956-01-24 I-methyl-z-carboxy-y-oxy derivatives of
US2621210A (en) * 1944-01-10 1952-12-09 Ciba Pharm Prod Inc Hexahydrophenanthrene carboxylic acids
US2687426A (en) * 1947-06-21 1954-08-24 Upjohn Co Process for the manufacture of a 1, 2-di-lower alkyl-2-carboxy-7 etherified hydroxy-1, 2, 3, 4, 9, 10-hexahydrophenanthrene
FR2081337A1 (en) * 1969-12-09 1971-12-03 Syntex Corp

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