CH485697A - Process for making new 9B, 10a steroids - Google Patents

Process for making new 9B, 10a steroids

Info

Publication number
CH485697A
CH485697A CH225069A CH225069A CH485697A CH 485697 A CH485697 A CH 485697A CH 225069 A CH225069 A CH 225069A CH 225069 A CH225069 A CH 225069A CH 485697 A CH485697 A CH 485697A
Authority
CH
Switzerland
Prior art keywords
sep
steroids
methyl
trien
acid
Prior art date
Application number
CH225069A
Other languages
German (de)
Inventor
Harmen Reerink Engbert
Louis Scholer Hendrik Frederik
Westerhof Pieter
Original Assignee
Hoffmann La Roche
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 Hoffmann La Roche filed Critical Hoffmann La Roche
Priority to CH225069A priority Critical patent/CH485697A/en
Publication of CH485697A publication Critical patent/CH485697A/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J7/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of two carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J1/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, not substituted in position 17 beta by a carbon atom, e.g. estrane, androstane
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J5/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, substituted in position 17 beta by a chain of two carbon atoms, e.g. pregnane and substituted in position 21 by only one singly bound oxygen atom, i.e. only one oxygen bound to position 21 by a single bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J75/00—Processes for the preparation of steroids in general

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Steroid Compounds (AREA)

Description

  

  Verfahren zur Herstellung von neuen     9#,.!Ocz-Steroiden       Die Erfindung betrifft ein Verfahren zur Herstellung  von neuen     9#,10"x-Steroiden    der Formel  
EMI0001.0003     
    in der     RI    Chlor oder Brom und R2 eine     Carbonylgruppe     oder eine der Gruppen  
EMI0001.0006     
    bedeuten, wobei R Wasserstoff, eine     Alkyl-,        Cycloalkyl-,          Cycloalkenyl-,        Aralkyl-,        Tetrahydropyranyl-    oder     Acyl-          C        Gruppe,    X     Wasserstoff,

          ein        Halogenatom        oder        eine        Hy-          droxy-    oder     Acyloxygruppe;        Y    Wasserstoff oder     OR     und Z Wasserstoff oder eine niedere     Alkyl,        Alkenyl-          oder        Alkinylgruppe    darstellen.  



  Ein durch das Symbol X dargestelltes Halogenatom  ist vorzugsweise ein     Fluoratom.    Als     Acylgruppen    kom  men     Acylreste    von Gesättigten oder ungesättigten     aliplia-          tischen,        cycloaliphatischen,        araliphatischen    oder aroma  tischen     Carbonsäuren    in Betracht, die     vorzuasweise   <B>1</B> bis  20     C-Atome    enthalten.

   Beispiele solcher Säuren sind:  Ameisensäure, Essigsäure,     Pivalinsäure,        PrOpiOnSäUre,       Buttersäure,     Capronsäure,        Önanthsäure,        ölsäure,        Palmi-          tinsäure,        Stearinsäure,    Bernsteinsäure,     Malonsäure,        Ben-          zoesäure.    Andere Beispiele für Reste R sind:

       Methyl,          Äthyl,        Propyl,        tert.-Butyl,        Cyclopentyl,        Cyclohexyl,        Ben-          zyl,        Cyclopenten-(1)-yl    und     l'-Äthoxy-cyclopentyl.     



  Durch das Symbol Z dargestellte niedere     Alkyl-,          Alkenyl-    und     Alkinylgruppen    enthalten vorzugsweise bis  zu<B>5</B>     C-Atome,    wie     Methyl,        Äthyl,        Propyl,        Isopropyl,          Butyl,        Isobutyl,        Amyl,        Vinyl,        Allyl,   <B>l'-</B> und     2'-Methallyl,          Äthinyl    und     Proparoyl.     



  Das     erfindunas-emässe    Verfahren ist dadurch gekenn  zeichnet, dass man ein der Formel<B>1</B> entsprechendes,  jedoch in     2-Stellung        unsubstituiertes        3-Keto--"\1,-1,1-9p,10a-          -Steroid    mit Chlor oder Brom behandelt und das erhal  tene     1,2-Dihalogen-steroid    anschliessend mit Basen, vor  zugsweise mit     Pyridin,        dehydrohalogeniert.     



  Die     erfindunosoemäss    erhältlichen neuen     9p,10a-Ste-          roide    der Formel<B>1</B> sind hormonal oder antihormonal  wirksam. So     zei2t    z. B. das     2!2-Chlor-17ot-methyl-17#-          -acetoxy-9#,102-androsta-1,4,6-trien-3-on    und das     2#-          -Brom   <B>-</B>     177#   <B>-</B>     methyl   <B>-</B>     17#   <B>-</B>     acetoxy-9#,10z-androsta-   <B>1,</B>     4,

  6-          -trien-3-on        antigonadotrope    Wirksamkeit und das     2-          -Chlor-9#,105c-Pre-na-1,4,6-trien-3,20-dion        anti-androgene     Wirksamkeit. Die Verfahrensprodukte können als Heil  mittel in Form pharmazeutischer Präparate Verwendung  finden.  



  In den     nachfolaenden    Beispielen sind die Tempera  turen in Celsiusgraden angegeben.  



       #   <B>C</B>  <I>Beispiel</I><B>1</B>  Zu einer     Lösune,    von<B>1,50<I>c</I></B>     17a-Methyl-        17#-acetoxy-          -9#,107.-androsta-1,4,6-trien-3-on    in<B>3</B> ml     Methylenchlo-          rid    und 40 ml Äther wurde bei -200 eine Lösung, von  <B>370</B> m- Chlor in<B>5</B>     mi        Eisessi-    Gegeben. Die     Mischuna     wurde<B>5</B> Stunden bei     -20"    Gehalten, dann auf Wasser  gegossen und mit     Methylenchlorid    extrahiert.

   Der mit  Wasser neutral Gewaschene Extrakt wurde Getrocknet,  eingedampft und der Rückstand mit<B>10</B>     mi        Pyridin   <B>j0</B> Mi  nuten bei Zimmertemperatur gehalten. Es wurde auf  Eiswasser verdünnte Salzsäure gegossen und mit Äther  extrahiert. Durch     Umkristallisieren    des Rohproduktes  aus Äther wurde 2-Chlor-172-methyl-17#-acetoxy-9#,105"-    
EMI0002.0001     
  
    -androsta-1,4,6-trien-3-on <SEP> erhalten. <SEP> Smp.: <SEP> 164 <SEP> bis <SEP> <B>1650.</B>
<tb>  -4370 <SEP> (in <SEP> Dioxan).
<tb>  



  <B>UV:</B> <SEP> Xma., <SEP> <B>216</B> <SEP> nm <SEP> <B><I>15</I> <SEP> 300</B>
<tb>  <B>265</B> <SEP> nm <SEP> <B><I>11500</I></B>
<tb>  <B>308</B> <SEP> nm <SEP> <B>10</B> <SEP> 400
<tb>  <I>Beispiel <SEP> 2</I>
<tb>  Analog <SEP> Beispiel <SEP> <B>1</B> <SEP> wurde <SEP> aus <SEP> 17a-Methyl-17p-hydroxy  -9ss,10a-androsta-1,4,6-trien-3-on <SEP> das <SEP> 2-Chlor-17a-methyl  -17ss-hydroxy-9p,10a-androsta-1,4,6-trien-3-on <SEP> erhalten.
<tb>  Schmelzpunkt: <SEP> 201 <SEP> bis <SEP> <B>2030</B> <SEP> (aus <SEP> Äther) <SEP> [a]25*D <SEP> =-4850
<tb>  (in <SEP> Dioxan).
<tb>  



  <I>Beispiel <SEP> <B>3</B></I>
<tb>  Analog <SEP> Beispiel <SEP> <B>1</B> <SEP> wurde <SEP> aus <SEP> 9ss,10a-Pregna-1,4,6  -trien-3,20-dion <SEP> das <SEP> 2-Chlor-9p,10a-Pregna-1,4,6-trien  -3,20-dion <SEP> erhalten. <SEP> Smp.:122 <SEP> bis <SEP> <B>12P,</B> <SEP> [a]2."D= <SEP> <B>3320</B>
<tb>  (in <SEP> Dioxan).
<tb>  



  <B>UV:</B> <SEP> 212 <SEP> nm <SEP> <B>a <SEP> <I>= <SEP> 15 <SEP> 000</I></B>
<tb>  <B>263</B> <SEP> nm <SEP> <B>e <SEP> = <SEP> 10 <SEP> 850</B>
<tb>  <B>309</B> <SEP> nm <SEP> <I>F <SEP> <B>=</B></I><B> <SEP> 10 <SEP> 100</B>
<tb>  <I>Beispiel <SEP> 4</I>
<tb>  Analog <SEP> Beispiel <SEP> <B>1</B> <SEP> wurde <SEP> unter <SEP> Verwendung <SEP> von
<tb>  Brom <SEP> als <SEP> Halogenierunggsmittel <SEP> aus <SEP> 17a-Methyl-17P-acet  oxy-9#,10a-androsta-1,4,6-trien-3-on <SEP> das <SEP> 2-Brom-17a  -methyl-17,p-acetoxy-9ss,10a-androsta-1,4,6-trien-3-on <SEP> er  halten. <SEP> Schmelzpunkt: <SEP> <B>132</B> <SEP> bis <SEP> 1340 <SEP> (aus <SEP> Äther-Hexan),
<tb>  [a]25. <SEP> <B>D <SEP> =-</B> <SEP> 4030 <SEP> (Dioxan).
<tb>  



  <B>UV: <SEP> 1.. <SEP> 218</B> <SEP> nm <SEP> <B>15 <SEP> 800</B>
<tb>  <B>268</B> <SEP> nm <SEP> 12 <SEP> <B>100</B>
<tb>  <B>309</B> <SEP> nm <SEP> <B>10 <SEP> 100</B>



  Process for the preparation of new 9 #,.! Ocz steroids The invention relates to a process for the preparation of new 9 #, 10 "x steroids of the formula
EMI0001.0003
    in RI chlorine or bromine and R2 a carbonyl group or one of the groups
EMI0001.0006
    where R is hydrogen, an alkyl, cycloalkyl, cycloalkenyl, aralkyl, tetrahydropyranyl or acyl C group, X is hydrogen,

          a halogen atom or a hydroxy or acyloxy group; Y represents hydrogen or OR and Z represents hydrogen or a lower alkyl, alkenyl or alkynyl group.



  A halogen atom represented by the symbol X is preferably a fluorine atom. Possible acyl groups are acyl radicals of saturated or unsaturated aliphatic, cycloaliphatic, araliphatic or aromatic carboxylic acids which preferably contain 1 to 20 carbon atoms.

   Examples of such acids are: formic acid, acetic acid, pivalic acid, propionic acid, butyric acid, caproic acid, enanthic acid, oleic acid, palmitic acid, stearic acid, succinic acid, malonic acid, benzoic acid. Other examples of radicals R are:

       Methyl, ethyl, propyl, tert-butyl, cyclopentyl, cyclohexyl, benzyl, cyclopentene- (1) -yl and l'-ethoxycyclopentyl.



  Lower alkyl, alkenyl and alkynyl groups represented by the symbol Z preferably contain up to 5 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, vinyl, allyl, etc. > l'- </B> and 2'-methallyl, ethynyl and proparoyl.



  The inventive method is characterized in that a 3-keto - "\ 1, -1,1-9p, 10a- - which corresponds to the formula <B> 1 </B> but is unsubstituted in the 2-position Treated steroid with chlorine or bromine and then obtained 1,2-dihalogenosteroids with bases, preferably with pyridine, dehydrohalogenated.



  The new 9p, 10a steroids of the formula <B> 1 </B> available according to the invention are hormonally or antihormonally effective. So zei2t z. B. the 2! 2-chloro-17ot-methyl-17 # - -acetoxy-9 #, 102-androsta-1,4,6-trien-3-one and the 2 # - -bromo <B> - </ B> 177 # <B> - </B> methyl <B> - </B> 17 # <B> - </B> acetoxy-9 #, 10z-androsta- <B> 1, </B> 4 ,

  6- -trien-3-one antigonadotropic activity and the 2- -chloro-9 #, 105c-Pre-na-1,4,6-triene-3,20-dione anti-androgenic activity. The products of the process can be used as medicinal products in the form of pharmaceutical preparations.



  In the following examples, the temperatures are given in degrees Celsius.



       # <B> C </B> <I> Example</I> <B> 1 </B> For a solution of <B> 1.50 <I> c </I> </B> 17a- Methyl- 17 # -acetoxy- -9 #, 107.-androsta-1,4,6-trien-3-one in 3 ml methylene chloride and 40 ml ether became a solution at -200 , from <B> 370 </B> m- chlorine in <B> 5 </B> with Eisessi- given. The mischuna was kept at -20 "for 5 hours, then poured into water and extracted with methylene chloride.

   The extract, washed neutral with water, was dried, evaporated, and the residue was kept at room temperature with 10 ml pyridine. It was poured into ice water diluted hydrochloric acid and extracted with ether. By recrystallizing the crude product from ether, 2-chloro-172-methyl-17 # -acetoxy-9 #, 105 "-
EMI0002.0001
  
    -androsta-1,4,6-trien-3-one <SEP> obtained. <SEP> Smp .: <SEP> 164 <SEP> to <SEP> <B> 1650. </B>
<tb> -4370 <SEP> (in <SEP> dioxane).
<tb>



  <B> UV: </B> <SEP> Xma., <SEP> <B> 216 </B> <SEP> nm <SEP> <B> <I> 15 </I> <SEP> 300 </ B>
<tb> <B> 265 </B> <SEP> nm <SEP> <B><I>11500</I> </B>
<tb> <B> 308 </B> <SEP> nm <SEP> <B> 10 </B> <SEP> 400
<tb> <I> Example <SEP> 2 </I>
<tb> Analogous to <SEP> Example <SEP> <B> 1 </B> <SEP> became <SEP> from <SEP> 17a-methyl-17p-hydroxy -9ss, 10a-androsta-1,4,6- trien-3-one <SEP> the <SEP> 2-chloro-17a-methyl-17ss-hydroxy-9p, 10a-androsta-1,4,6-trien-3-one <SEP>.
<tb> Melting point: <SEP> 201 <SEP> to <SEP> <B> 2030 </B> <SEP> (from <SEP> ether) <SEP> [a] 25 * D <SEP> = -4850
<tb> (in <SEP> dioxane).
<tb>



  <I> Example <SEP> <B>3</B> </I>
<tb> Analogous to <SEP> example <SEP> <B> 1 </B> <SEP> became <SEP> from <SEP> 9ss, 10a-Pregna-1,4,6 -trien-3,20-dione < SEP> the <SEP> 2-chloro-9p, 10a-pregna-1,4,6-triene -3,20-dione <SEP> obtained. <SEP> Smp.:122 <SEP> to <SEP> <B> 12P, </B> <SEP> [a] 2. "D = <SEP> <B> 3320 </B>
<tb> (in <SEP> dioxane).
<tb>



  <B> UV: </B> <SEP> 212 <SEP> nm <SEP> <B> a <SEP> <I> = <SEP> 15 <SEP> 000 </I> </B>
<tb> <B> 263 </B> <SEP> nm <SEP> <B> e <SEP> = <SEP> 10 <SEP> 850 </B>
<tb> <B> 309 </B> <SEP> nm <SEP> <I> F <SEP> <B>=</B></I> <B> <SEP> 10 <SEP> 100 </ B>
<tb> <I> Example <SEP> 4 </I>
<tb> Similar to <SEP> Example <SEP> <B> 1 </B> <SEP> was <SEP> under <SEP> using <SEP> from
<tb> bromine <SEP> as <SEP> halogenating agent <SEP> from <SEP> 17a-methyl-17P-acet oxy-9 #, 10a-androsta-1,4,6-trien-3-one <SEP> das <SEP> 2-bromo-17a-methyl-17, p-acetoxy-9ss, 10a-androsta-1,4,6-trien-3-one <SEP> are obtained. <SEP> Melting point: <SEP> <B> 132 </B> <SEP> to <SEP> 1340 <SEP> (from <SEP> ether-hexane),
<tb> [a] 25. <SEP> <B> D <SEP> = - </B> <SEP> 4030 <SEP> (dioxane).
<tb>



  <B> UV: <SEP> 1 .. <SEP> 218 </B> <SEP> nm <SEP> <B> 15 <SEP> 800 </B>
<tb> <B> 268 </B> <SEP> nm <SEP> 12 <SEP> <B> 100 </B>
<tb> <B> 309 </B> <SEP> nm <SEP> <B> 10 <SEP> 100 </B>

Claims (1)

<B>PATENTANSPRUCH</B> Verfahren zur Herstellung von neuen 9p,102-Steroi- den der Formel EMI0002.0004 in der RI Chlor oder Brom und R2 eine Carbonylgruppe oder eine der Gruppen EMI0002.0007 bedeuten, wobei R Wasserstoff, eine Alkyl, Cycloalkyl- Cycloalkenyl, Aralkyl-, Tetrahydropyranyl- oder Acyl- gruppe, X Wasserstoff, ein Halogenatom oder eine Hy- droxy- oder Acyloxygruppe; <B> PATENT CLAIM </B> Process for the production of new 9p, 102 steroids of the formula EMI0002.0004 in RI chlorine or bromine and R2 a carbonyl group or one of the groups EMI0002.0007 where R is hydrogen, an alkyl, cycloalkyl, cycloalkenyl, aralkyl, tetrahydropyranyl or acyl group, X is hydrogen, a halogen atom or a hydroxy or acyloxy group; Y Wasserstoff oder OR und Z Wasserstoff oder eine niedere Alkyl-, Alkenyl- oder Alkinylgruppe darstellen, dadurch gekennzeichnet, dass man ein der Formel I ent sprechendes, jedoch in 2-Stellung unsubstituiertes 3-Keto- -A1,4,11-9#, 10o#-Steroid mit Chlor oder Brom behandelt und das so erhaltene 1,2-Dihalo-en-steroid anschliessend mit Basen, Y represents hydrogen or OR and Z represents hydrogen or a lower alkyl, alkenyl or alkynyl group, characterized in that one of the formula I, but unsubstituted in the 2-position 3-keto -A1,4,11-9 # , 10o # steroid treated with chlorine or bromine and the 1,2-dihalo-en-steroid thus obtained then with bases, dehydrohalogeniert. <B>UNTERANSPRÜCHE</B> <B>1.</B> Verfahren nach Patentanspruch, dadurch gekenn zeichnet, dass man die Dehydrohalogenierung mittels ZD cl Pyridin durchführt. 2. Verfahren nach Patentanspruch und Unteran spruch<B>1,</B> dadurch gekennzeichnet, dass man 17,z-Methyl- -17#-acetoxy-(oder -hydroxy)-9#,1%-androsta-1,4,6-trien- -3-on als Ausgangsstoff verwendet. <B>0</B> dehydrohalogenated. <B> SUBClaims </B> <B> 1. </B> Method according to patent claim, characterized in that the dehydrohalogenation is carried out using ZD cl pyridine. 2. The method according to claim and sub-claim <B> 1, </B> characterized in that 17, z-methyl- -17 # -acetoxy- (or -hydroxy) -9 #, 1% -androsta-1, 4,6-trien- -3-one used as a starting material. <B> 0 </B>
CH225069A 1965-07-06 1965-07-06 Process for making new 9B, 10a steroids CH485697A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CH225069A CH485697A (en) 1965-07-06 1965-07-06 Process for making new 9B, 10a steroids

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH948565A CH475224A (en) 1965-07-06 1965-07-06 Process for making new 9B, 10x steroids
CH225069A CH485697A (en) 1965-07-06 1965-07-06 Process for making new 9B, 10a steroids

Publications (1)

Publication Number Publication Date
CH485697A true CH485697A (en) 1970-02-15

Family

ID=4352488

Family Applications (5)

Application Number Title Priority Date Filing Date
CH225369A CH485698A (en) 1965-07-06 1965-07-06 Process for making new 9B, 10a steroids
CH225269A CH483416A (en) 1965-07-06 1965-07-06 Process for making new 9B, 10x steroids
CH225469A CH490356A (en) 1965-07-06 1965-07-06 Process for the manufacture of new 9B-10a steroids
CH225069A CH485697A (en) 1965-07-06 1965-07-06 Process for making new 9B, 10a steroids
CH948565A CH475224A (en) 1965-07-06 1965-07-06 Process for making new 9B, 10x steroids

Family Applications Before (3)

Application Number Title Priority Date Filing Date
CH225369A CH485698A (en) 1965-07-06 1965-07-06 Process for making new 9B, 10a steroids
CH225269A CH483416A (en) 1965-07-06 1965-07-06 Process for making new 9B, 10x steroids
CH225469A CH490356A (en) 1965-07-06 1965-07-06 Process for the manufacture of new 9B-10a steroids

Family Applications After (1)

Application Number Title Priority Date Filing Date
CH948565A CH475224A (en) 1965-07-06 1965-07-06 Process for making new 9B, 10x steroids

Country Status (1)

Country Link
CH (5) CH485698A (en)

Also Published As

Publication number Publication date
CH483416A (en) 1969-12-31
CH485698A (en) 1970-02-15
CH475224A (en) 1969-07-15
CH490356A (en) 1970-05-15

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