CH245880A - Process for the preparation of a new oxyhydrophenanthrene derivative. - Google Patents

Process for the preparation of a new oxyhydrophenanthrene derivative.

Info

Publication number
CH245880A
CH245880A CH245880DA CH245880A CH 245880 A CH245880 A CH 245880A CH 245880D A CH245880D A CH 245880DA CH 245880 A CH245880 A CH 245880A
Authority
CH
Switzerland
Prior art keywords
preparation
new
derivative
methoxy
ethyl
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 CH245880A publication Critical patent/CH245880A/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     Oxyhydrophenanthren-Derivat    gelangen  kann, wenn man eine     1-Äthyliden-2-Äthyl-          7-metlioxy    -1,2,3,4 -     tetrahydrophenanthren-    2     -          carbonsäure    zwecks Überführung der     Äthyl-          idengruppierung    in einen     Äthylrest    mit hy  drierenden     Mitteln    behandelt.  



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



  Das neue Verfahrensprodukt,     die        östrogen       wirksame     1,2-Diäthyl-7-methoxy-1,2,3,4-tetra-          hydrophenanthren-2-carbonsäure    vom F. 183  bis<B>185',</B> soll therapeutische Verwendung finden  oder als Zwischenprodukt zur Herstellung  therapeutisch verwendbarer     Verbindungen     dienen.  



  <I>Beispiel:</I>  4 Gewichtsteile 1-     Äthyliden    - 2 -     äthyl    - 7        methoxy-1,2,3,4-tetrahydrophenanthren-2-car-          bonsäure    vom .F.<B>198-2000</B> der Formel  
EMI0001.0025     
    (erhalten z.

   B. aus 1-geto-2-äthyl-7-methoxy       1,2,3J4-tetrahydrophenanthren-2-carboDsäure-          methylester    durch     Grignardierung    mit Äthyl  magnesiumbromid, Wasserabspaltung aus dem  so erhaltenen     1,2-Diäthyl-l-oxy-7-methoxy-          1,    2, 3,4-     tetrahydrophenanthren-    2     -carbon    s     äure-          methylester    vom F.<B>131-1320</B> und an-    schliessende     Verseifung        mitgaliumhydroxyd    bei  <B>1600)</B> werden in einer Lösung von 10 Volu  menteilen 2     n-Natronlauge,

      150     Volumenteilen     Wasser und 100 Volumenteilen     Äthanol    in 4  Gegenwart von 10     Gewichtsteilen    eines     Nickel-          katalysators    hydriert. Nach Aufnahme der für  etwa 1,5     Moläquivalente    berechneten Menge           Wasserstoff    bleibt die Hydrierung stehen. Man  filtriert vom Nickel ab und versetzt das klare  Filtrat mit verdünnter Salzsäure.

   Das ausge  fallene Produkt ergibt, aus Aceton und    Methanol umkristallisiert, die     östrogen    wirk  same     1,2-Diäthyl-7-methoxy-1,2,3,4-tetra-          hydrophena.ntbren-2-carbonsäure    der Formel  
EMI0002.0005     
         in    Form farbloser     Kristalle    vom F. 183 bis  185   nebst einer geringen Menge eines un  wirksamen     Diastereoisomeren    vom F. 196 bis  <B>1980.</B>



  Process for the preparation of a new oxyhydrophenanthrene derivative. It has been found that a new oxyhydrophenanthrene derivative can be obtained if a 1-ethylidene-2-ethyl-7-metlioxy -1,2,3,4-tetrahydrophenanthrene-2-carboxylic acid is used to convert the ethylidene group into treated an ethyl residue with hydrating agents.



  Catalytic hydrogenation, for example, can be used to convert the ethylidene group into the ethyl radical.



  The new process product, the estrogenically active 1,2-diethyl-7-methoxy-1,2,3,4-tetrahydrophenanthrene-2-carboxylic acid from F. 183 to <B> 185 ', </B> is intended for therapeutic use find or serve as an intermediate for the preparation of therapeutically useful compounds.



  <I> Example: </I> 4 parts by weight of 1-ethylidene - 2 - ethyl - 7 methoxy-1,2,3,4-tetrahydrophenanthrene-2-carboxylic acid from F.F. 198-2000 </ B > the formula
EMI0001.0025
    (received e.g.

   B. from 1-geto-2-ethyl-7-methoxy 1,2,3J4-tetrahydrophenanthrene-2-carbodic acid methyl ester by Grignardation with ethyl magnesium bromide, elimination of water from the 1,2-diethyl-l-oxy-7- Methoxy-1, 2, 3,4-tetrahydrophenanthrene-2-carbonic acid methyl ester of F. 131-1320 and subsequent saponification with galium hydroxide at 1600) are in a solution of 10 parts by volume of 2N sodium hydroxide solution,

      150 parts by volume of water and 100 parts by volume of ethanol 4 hydrogenated in the presence of 10 parts by weight of a nickel catalyst. After the amount of hydrogen calculated for about 1.5 molar equivalents has been taken up, the hydrogenation stops. The nickel is filtered off and the clear filtrate is mixed with dilute hydrochloric acid.

   The precipitated product, recrystallized from acetone and methanol, gives the estrogenically active 1,2-diethyl-7-methoxy-1,2,3,4-tetra-hydrophena.ntbren-2-carboxylic acid of the formula
EMI0002.0005
         in the form of colorless crystals from mp 183 to 185 together with a small amount of an inactive diastereoisomer from mp 196 to 1980.

Claims (1)

PATENTANSPRUCH: Verfahren zur Herstellung eines neuen Oxyhydrophenanthren-Derivates, dadurch ge kennzeichnet, dass man eine 1-Äthyliden-2- äthyl - 7 - methoxy - 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-ethyl-7-methoxy-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 neue Verfahrensprodukt, die östrogen wirksame 1,2-Diäthyl-7-methoxy-1,2,3,4-tetra- hydrophenanthren-2-carbonsäure vom F. 183 bis 18v , solltherapeutische Verwendungfinden oder als Zwischenprodukt zur Herstellung therapeutisch verwendbarer Verbindungen dienen. UNTERANSPRüCHE: 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 Hydrierung in Alkalilauge in Gegenwart eines Nickel katalysators vornimmt. The new process product, the estrogenically active 1,2-diethyl-7-methoxy-1,2,3,4-tetra-hydrophenanthrene-2-carboxylic acid from F. 183 to 18v, should find therapeutic use or serve as an intermediate product for the preparation of therapeutically useful compounds . SUBClaims: 1. 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.
CH245880D 1944-01-10 1944-01-10 Process for the preparation of a new oxyhydrophenanthrene derivative. CH245880A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH242609T 1944-01-10
CH245880T 1944-01-10

Publications (1)

Publication Number Publication Date
CH245880A true CH245880A (en) 1946-11-30

Family

ID=25728704

Family Applications (1)

Application Number Title Priority Date Filing Date
CH245880D CH245880A (en) 1944-01-10 1944-01-10 Process for the preparation of a new oxyhydrophenanthrene derivative.

Country Status (1)

Country Link
CH (1) CH245880A (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

Similar Documents

Publication Publication Date Title
CH245880A (en) Process for the preparation of a new oxyhydrophenanthrene derivative.
CH250806A (en) Process for the preparation of a new oxyhydrophenanthrene derivative.
DE2218647A1 (en) Secretolytic n-(trans-4-hydroxycyclohexyl)-2-amino-3,5- - dibromobenzylamine prepn - by redn of n-(2-amino-3,5-dibromobenzylide
CH245881A (en) Process for the preparation of a new oxyhydrophenanthrene derivative.
CH245879A (en) Process for the preparation of a new oxyhydrophenanthrene derivative.
CH242609A (en) Process for the preparation of a new oxyhydrophenanthrene derivative.
CH245882A (en) Process for the preparation of a new oxyhydrophenanthrene derivative.
CH250810A (en) Process for the preparation of a new oxyhydrophenanthrene derivative.
CH250809A (en) Process for the preparation of a new oxyhydrophenanthrene derivative.
CH250805A (en) Process for the preparation of a new oxyhydrophenanthrene derivative.
CH254446A (en) Process for the preparation of a new oxyhydrophenanthrene derivative.
CH250808A (en) Process for the preparation of a new oxyhydrophenanthrene derivative.
CH250807A (en) Process for the preparation of a new oxyhydrophenanthrene derivative.
CH248378A (en) Process for the preparation of a new oxyhydrophenanthrene derivative.
AT257571B (en) Process for the preparation of the new N-benzyl-α, α-dimethyl-β- (p-fluorophenyl) ethylamine and its salts
AT224625B (en) Process for the production of new amino alcohols and their salts
DE744610C (en) Process for the preparation of ª ‰ -alanine
AT160826B (en) Process for the preparation of derivatives of androstenediol.
AT157574B (en) Process for the preparation of butanediol- (1.3).
CH262164A (en) Process for the preparation of a new oxyhydrophenanthrene derivative.
CH262163A (en) Process for the preparation of a new oxyhydrophenanthrene derivative.
CH262162A (en) Process for the preparation of a new oxyhydrophenanthrene derivative.
CH254452A (en) Process for the preparation of a new oxyhydrophenanthrene derivative.
CH254451A (en) Process for the preparation of a new oxyhydrophenanthrene derivative.
CH254447A (en) Process for the preparation of a new oxyhydrophenanthrene derivative.