DE2609694C3 - 17 a- (3-Hydroxpropyl) -17 ß-hydroxy-7 a-thioalkanoyl-4-androsten-3-ones and process for their preparation - Google Patents

17 a- (3-Hydroxpropyl) -17 ß-hydroxy-7 a-thioalkanoyl-4-androsten-3-ones and process for their preparation

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Publication number
DE2609694C3
DE2609694C3 DE19762609694 DE2609694A DE2609694C3 DE 2609694 C3 DE2609694 C3 DE 2609694C3 DE 19762609694 DE19762609694 DE 19762609694 DE 2609694 A DE2609694 A DE 2609694A DE 2609694 C3 DE2609694 C3 DE 2609694C3
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Prior art keywords
hydroxy
androsten
hydroxypropyl
ones
preparation
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Expired
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DE19762609694
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German (de)
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DE2609694B2 (en
DE2609694A1 (en
Inventor
Bernhard Dr. 4750 Unna Krieger
Rainer Dr. 4619 Bergkamen Philippson
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Bayer Pharma AG
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Schering AG
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Priority to DE19762609694 priority Critical patent/DE2609694C3/en
Priority to AU22633/77A priority patent/AU513542B2/en
Priority to IE451/77A priority patent/IE44711B1/en
Priority to CH261377A priority patent/CH631462A5/en
Priority to LU76883A priority patent/LU76883A1/xx
Priority to US05/773,982 priority patent/US4118488A/en
Priority to DD7700197658A priority patent/DD128659A5/en
Priority to AT0141377A priority patent/AT365611B/en
Priority to SU772457127A priority patent/SU755202A3/en
Priority to IL51586A priority patent/IL51586A/en
Priority to NL7702369A priority patent/NL7702369A/en
Priority to ES456543A priority patent/ES456543A1/en
Priority to JP2370377A priority patent/JPS52111552A/en
Priority to CS148077A priority patent/CS200507B2/en
Priority to SE7702455A priority patent/SE420732B/en
Priority to BE175469A priority patent/BE852089A/en
Priority to HUSC000597 priority patent/HU181969B/en
Priority to DK96177A priority patent/DK146856C/en
Priority to CA273,185A priority patent/CA1078826A/en
Priority to FR7706567A priority patent/FR2342990A1/en
Priority to GB9464/77A priority patent/GB1579298A/en
Publication of DE2609694A1 publication Critical patent/DE2609694A1/en
Publication of DE2609694B2 publication Critical patent/DE2609694B2/en
Application granted granted Critical
Publication of DE2609694C3 publication Critical patent/DE2609694C3/en
Priority to CS786764A priority patent/CS200509B2/en
Priority to AT0180980A priority patent/AT370110B/en
Priority to CH306781A priority patent/CH629225A5/en
Priority to DK403382A priority patent/DK403382A/en
Expired legal-status Critical Current

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    • 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
    • C07J1/0003—Androstane derivatives
    • C07J1/0033—Androstane derivatives substituted in position 17 alfa and 17 beta
    • 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
    • C07J1/0051—Estrane derivatives
    • C07J1/0081—Substituted in position 17 alfa and 17 beta
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J31/00—Normal steroids containing one or more sulfur atoms not belonging to a hetero ring
    • C07J31/003—Normal steroids containing one or more sulfur atoms not belonging to a hetero ring the S atom directly linked to a ring carbon atom of the cyclopenta(a)hydrophenanthrene skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J41/00—Normal steroids containing one or more nitrogen atoms not belonging to a hetero ring
    • C07J41/0033—Normal steroids containing one or more nitrogen atoms not belonging to a hetero ring not covered by C07J41/0005
    • C07J41/0038—Normal steroids containing one or more nitrogen atoms not belonging to a hetero ring not covered by C07J41/0005 with an androstane skeleton, including 18- or 19-substituted derivatives, 18-nor derivatives and also derivatives where position 17-beta is substituted by a carbon atom not directly bonded to a further carbon atom and not being part of an amide group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J43/00—Normal steroids having a nitrogen-containing hetero ring spiro-condensed or not condensed with the cyclopenta(a)hydrophenanthrene skeleton
    • C07J43/003—Normal steroids having a nitrogen-containing hetero ring spiro-condensed or not condensed with the cyclopenta(a)hydrophenanthrene skeleton not condensed
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J51/00—Normal steroids with unmodified cyclopenta(a)hydrophenanthrene skeleton not provided for in groups C07J1/00 - C07J43/00
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J53/00—Steroids in which the cyclopenta(a)hydrophenanthrene skeleton has been modified by condensation with a carbocyclic rings or by formation of an additional ring by means of a direct link between two ring carbon atoms, including carboxyclic rings fused to the cyclopenta(a)hydrophenanthrene skeleton are included in this class
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J53/00—Steroids in which the cyclopenta(a)hydrophenanthrene skeleton has been modified by condensation with a carbocyclic rings or by formation of an additional ring by means of a direct link between two ring carbon atoms, including carboxyclic rings fused to the cyclopenta(a)hydrophenanthrene skeleton are included in this class
    • C07J53/002—Carbocyclic rings fused
    • C07J53/004—3 membered carbocyclic rings
    • C07J53/007—3 membered carbocyclic rings in position 6-7

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

Description

Die Erfindung betrifft 17«-(3-HydroxypropyI)-17/?- hydroxy-7a-thioalkaiioyl-4-androsten-3-one und ein Verfahren zu deren Herstellung.The invention relates to 17 «- (3-HydroxypropyI) -17 /? - hydroxy-7a-thioalkaiioyl-4-androsten-3-one and a Process for their manufacture.

Unter der Gruppierung Thioaikanoyl sind solche Gruppen zu verstehen, die sich von niederen Thioalkansäuren mit bis zu 6 C-Atomen, wie z. B. der Thioessig- und derThiopropionsäure, ableiten.Under the grouping thioaikanoyl are such Understand groups that differ from lower thioalkanoic acids with up to 6 carbon atoms, such as. B. the thioacetic and the thiopropionic acid.

Die erfindungsgemäßen Verbindungen selbst besitze J pharmakologisch wertvolle Eigenschaften, und insbesondere ist die 7e-Thioacetylverbindung vorteilhaft als Zwischenprodukt zur Herstellung des bekannten Aidosteronblockers Spironolacton [3-(17/?-Hydroxy-7<x-thioacetyl-3-oxo-4-and rosten · 17«-yl)-propionsäurelacionl geeignet.The compounds according to the invention themselves have pharmacologically valuable properties, and the 7e-thioacetyl compound is particularly advantageous as an intermediate for the production of the well-known aidosterone blocker spironolactone [3- (17 /? - Hydroxy-7 <x-thioacetyl-3-oxo-4-and rust · 17 «-yl) -propionic acid lacionl suitable.

Aus der DE-OS 22 51 476 ist ein Verfahren bekannt, bei dem ^-(3-Keto-17^-hydroxy-4,6-androstadien-17ayl)-propionaldchyddialkyl- oder -alkylenacetale mit Thiocarbonsäuren unter Zusatz von Wasser und einem mit Wasser mischbaren organischen Lösungsmittel zu den entsprechenden 0-(3-Keto-7«-thioacetyl-l70-hydroxy-4-andrcmen-17a-yl)-propionaldehyddialkyl- oder -alkylenaretalcn umgesetzt werden, die dann in saurer Lösung zu den 0-{3-Keto-7*-lhioacety!-l7/Miydroxy-4-androsten-1 7λ ylj-propionsäure-y-lactonen oxydiert werden.From DE-OS 22 51 476 a method is known at the ^ - (3-keto-17 ^ -hydroxy-4,6-androstadien-17ayl) -propionaldchyddialkyl- or alkylene acetals with thiocarboxylic acids with the addition of water and one water-miscible organic solvents to the corresponding 0- (3-keto-7 «-thioacetyl-170-hydroxy-4-andrcmen-17a-yl) -propionaldehyde dialkyl or -alkylenaretalcn are implemented, which are then converted into acidic Solution to the 0- {3-keto-7 * -lhioacety! -L7 / miydroxy-4-androstene-1 7λ ylj-propionic acid-y-lactones oxidized will.

Das bekannte Verfahren hat jedoch den Nachteil, daß die als Ausgangsmaterial verwendeten 17 Propioaldehyd-acetale nmr schwer zugänglich sind.However, the known process has the disadvantage that the 17 propioaldehyde acetals used as starting material nmr are difficult to access.

Des weiteren liegen die mit dem erfindungsgemaßen Verfahren erhaltenen Gesamtausbeuten an Spironolac-(on deutlich über den Ausbeuten, die mit dem bekannten Verfahren erhalten werden.Furthermore, the total yields of spironolac- (on) obtained with the process according to the invention are well above the yields that can be obtained with the known process.

Es wurde nun gefunden, daß man 17« (3-Hydroxypro pyl)-l 70 hydroxy 4,6-androstadienJ-Qn in einem protischen Lösungsmittel oder Gemischen davon gegebenenfalls in Gegenwart tines Lösungsvermittlers bei Temperaturen von 0* bis /ur Siedehitze mit einer Thioalkansäure leicht umsetzen kann.It has now been found that 17 "(3-Hydroxypro pyl) -l 70 hydroxy 4,6-androstadienJ-Qn in a protic Solvents or mixtures thereof, if appropriate in the presence of a solubilizer Temperatures from 0 * to / ur boiling point with a Thioalkanoic acid can easily convert.

Der Verlauf der erfindungsgemißen Reaktion ist durchaus überraschend, da /u erwarten gewesen wäre, daß auch gleich/eilig eine Fsterbildung am Kohlenstoff atom C - 2J auf 1 ritt f'ührt man namlk h die Thioacetylicriing unter ilen Bedingungen der UX PS M 21 610 durch, so erhäii man liberwiegend da« C- 2 Ί acetylierto Prmlulr t. wie folgendes Beispiel zeigtThe course of the reaction according to the invention is quite surprising, since it would have been expected that the formation of a window at the carbon atom C-2J would also take place immediately if the thioacetylation is carried out under the conditions of UX PS M 21 610 , one obtains predominantly the "C-2" acetylated pre-fluid. as the following example shows

2 g I7v(l Hvdroxypropyl)-17/MIy(Im^y 4.6androsliiciien Jon werden in 1,8 mi Thioessigsäiirc· 30 Minuten bei 900C erhitzt Danach wird die überschüssige Thioessigsäure durch Destillation unter vermindertem Druck entfernt und der Rückstand chromatographiert Es werden 1,1 g 17«-(3-AcetoxypropyI)-17/?-hydroxy-7«-thioacetyl-4-androsten-3-on erhalten.2 g I7v (l Hvdroxypropyl) -17 / MIY (Im ^ y 4.6androsliiciien Jon be in 1.8 mi Thioessigsäiirc x 30 minutes at 90 0 C. Thereafter, the heated excess thioacetic acid was removed by distillation under reduced pressure and the residue chromatographed are 1.1 g of 17 "- (3-acetoxypropyl) -17 /? - hydroxy-7" -thioacetyl-4-androsten-3-one were obtained.

Das für das erfindungsgemäße Verfahren verwendete Ausgangsmaterial 17«-{3-Hydroxypropyl)-170-hydroxy-4,6-androstadien-3-on kann nach an sich bekannten Methoden aus 17a-{3-Hydroxypropy!)-17/?-hydroxy-4-androsten-3-on, z. B. durch Dehydrierung mit Chloranil, hergesteüt werden (US-PS 31 37 690).The starting material used for the process according to the invention 17 "- {3-hydroxypropyl) -170-hydroxy-4,6-androstadien-3-one can according to methods known per se from 17a- {3-Hydroxypropy!) - 17 /? - hydroxy-4-androsten-3-one, z. B. by dehydration with chloranil, are hergesteüt (US-PS 31 37 690).

Zur Durchführung des erfindungsgemaßen Verfahrens wird das 17a-{3-HydroxypropyI)-17/i-hydroxy-4,6-androstadien in einem protischen Lösungsmittel gelöstTo carry out the process according to the invention, 17a- {3-hydroxypropyl) -17 / i-hydroxy-4,6-androstadiene is used dissolved in a protic solvent

is wobei auch inerte Lösungsmittel zugesetzt werden können.is whereby inert solvents can also be added.

Als protische Lösungsmittel seien insbesondere genannt niedere Alkanole wie Methanol, Äthanol und Butanol, cyclische Äther wie Tetrahydrofuran und Dioxan, niedere Ketone wie Aceton und Säurederivate wie Dimethylformamid. Es kennen aber auch Gemische dieser Lösungsmittel untereinander eingesetzt werden. Der Zusatz von inerten Lösungsmittel, die als Lösungsvermittler dienen, wie z. B. Heptan, Benzol und Diisopropyläther, stön den erfindungsgemaßen Reaktionsverlauf nichtProtic solvents that may be mentioned in particular are lower alkanols such as methanol, ethanol and Butanol, cyclic ethers such as tetrahydrofuran and dioxane, lower ketones such as acetone and acid derivatives like dimethylformamide. But there are also mixtures these solvents are used with one another. The addition of inert solvents that act as Serve solubilizers, such as. B. heptane, benzene and diisopropyl ether, disturb the course of the reaction according to the invention not

Zu dem so gelösten 17*-(3 Hydroxypropyl)-170-hydroxy-4,6-androstadien gibt man die Thioalkansäure im Oberschuß. An sich würde schon eine Menge von 1,1 Moläquivalcnt ausreichen, jedoch ist es zweckmäßig, einen etwas größeren Überschuß anzuwenden, vorzugsweise 2-5 Moläquivalente.To the 17 * - (3 hydroxypropyl) -170-hydroxy-4,6-androstadiene thus dissolved you give the thioalkanoic acid in excess. In itself it would be an amount of 1.1 Molar equivalents are sufficient, but it is advisable to use a somewhat larger excess, preferably 2-5 molar equivalents.

Die Reaktion läuft an sich schon bei Temperaturen unterhalb Raumtemperatur ab. Es ist jedoch vorteilhaft.The reaction takes place even at temperatures below room temperature. However, it is beneficial.

js das Reaktionsgemisch zu erwärmen. Bei Temperaturen im Bereich des Siedepunktes ist die Reaktion bereits nach einer Stunde beendet js to heat the reaction mixture. At temperatures in the range of the boiling point, the reaction has ended after just one hour

Das Reaktionsprodukt wird nach an sich bekannten Methoden wie Filtration abgetrennt und beispielsweise durch Chromatographie und/oder UmkristaUisation gereinigtThe reaction product is separated off by methods known per se, such as filtration, and for example purified by chromatography and / or recrystallization

Insbesondere ist die erfindungsgemäße Verbindung 17«-(3-Hydroxypropyl)-17^-hydroxy-7(*-thioacetyl-4-androsten-3-on als Zwischenprodukt zur HerstellungIn particular, the compound according to the invention is 17 "- (3-hydroxypropyl) -17 ^ -hydroxy-7 (* - thioacetyl-4-androsten-3-one as an intermediate product for manufacture

as des bekannten Spironolactons geeignet. Hierzu wird das 17«-(3-Hydroxypropyl)-170-hydroxy-7«-thioacetyl-4-androsten-3-on nach an sich bekannten Methoden mit Chromsäure unter Lactonisierung zum Spironolacton oxydiert, wofür das folgende Beispiel steh'.: as of the well-known spironolactone. For this purpose, the 17 "- (3-hydroxypropyl) -170-hydroxy-7" -thioacetyl-4-androsten-3-one is oxidized by methods known per se with chromic acid with lactonization to give spironolactone, for which the following example stands:

y> 03 g l7«-(3-Hydroxypropyl)-17/?-hydroxy-7*-lhioacetj»l-4-andro»ien-3-on werden bei 0"C in 10 ml Aceton suspendiert. Zu dieser Suspension läßt man langsam 032 ml Jones-Reagens zutropfen, so daß die Temperatur 5eC nicht überschreitet. Man rührt I Stunde bei 0-5° C. Das überschüssige Jones-Reagens wird mit Methanol zerstört, die ausgefallenen Chromsalare abfiltriert, das Filtrat zur Trockne eingeengt und durch Zugabe von Methanol kristallisier*. Nach Absaugen und Trocknen erhält man 038 g 3(170-Hydroxy-7«-thioace-y> 03 g of 17 "- (3-hydroxypropyl) -17 /? - hydroxy-7 * -lhioacetj" l-4-andro »ien-3-one are suspended at 0" C in 10 ml of acetone. This suspension is added added slowly 032 ml of Jones reagent are added dropwise so that the temperature does not exceed 5 e C. the mixture is stirred I hour at 0-5 ° C. the excess Jones reagent is destroyed with methanol, filtered, the precipitated Chromsalare, the filtrate concentrated to dryness and crystallize by adding methanol. After filtering off with suction and drying, 038 g of 3 (170-hydroxy-7'-thioaceous

Mt tyl-3-oxo-4-androsten-l7<vyl)-propionsäurelacton vom Schmelzpunkt 202 - 205" C. Mt tyl-3-oxo-4-androsten-l7 <vyl) -propionic acid lactone with a melting point of 202-205 "C.

Die nachfolgenden Beispiele sollen das crfindungsgemäße Verfahren erläutern.The following examples are intended to improve the Explain the procedure.

H e i s ρ i e I IH e i s ρ i e I I

I g 17t-(J-Hydroxvpropyl) 17/}-hydroxy-4,6-anclro Stadien )-on wird in 5 ml Methanol gelöst, /u dieser Losung werden in riet Wärme 0.4 J ml Thioessigsäure·I g of 17t- (J-hydroxypropyl) 17 /} - hydroxy-4,6-anclro Stages) -one is dissolved in 5 ml of methanol, / u this Dissolve in advised heat 0.4 J ml of thioacetic acid

gegeben. Anschließend wird das Reaktionsgemisch 1 Stunde am Sieden gehalten. Danach wird das Reaktionsgemisch unter vermindertem Druck zur Trockne eingeengt Der Rückstand wird in Aceton zur Kristallisation gebracht Die Kristalle werden abgesaugt und getrocknet Man erhält 0,75 g 17«-(3-Hydroxypropyl)-l70-hydroxy-7«-thioacetyl-4-androsten-3-on vom Schmelzpunkt 187-192° C
UV:€2M = 18 400.given. The reaction mixture is then kept boiling for 1 hour. The reaction mixture is then concentrated to dryness under reduced pressure. The residue is crystallized in acetone. The crystals are filtered off with suction and dried. 0.75 g of 17 "- (3-hydroxypropyl) -170-hydroxy-7" -thioacetyl-4- androsten-3-one with a melting point of 187-192 ° C
UV: € 2M = 18 400.

Beispiel 2Example 2

3 g 17«-{3-Hydroxypropyl)-17ß-hydroxy-4,6-androstadien-3-on werden in 15 ml Aceton und 6 ml Methanol suspendiert, mit 1,29 ml Thioessigsäure versetzt und 45 Minuten zum Sieden erhitzt Die Aufarbeitung nach Beendigung der Reaktion erfolgt analog Beispiel 1. Man erhält 2,4 g 17*-(3-HydroxvpropyI)-17ß-hydroxy-7athioacetyl-4-androsten-3-on vom Schmelzpunkt 187-192°C3 g of 17 "- {3-hydroxypropyl) -17 [beta] -hydroxy-4,6-androstadien-3-one are suspended in 15 ml of acetone and 6 ml of methanol, treated with 1.29 ml of thioacetic acid and 45 Heated to the boil for minutes. After the reaction has ended, work-up is carried out analogously to Example 1. Man receives 2.4 g of 17 * - (3-HydroxvpropyI) -17ß-hydroxy-7athioacetyl-4-androsten-3-one from melting point 187-192 ° C

UV: 6239 = 18 400.UV: 6239 = 18,400.

Beispiel 3Example 3

0,5 g 17«-(3- Hydraxypropyl)-170-hydroxy-4,6-androstadien-3-on wird in 2JS ml Tetrahydrofuran und 1 ml Methanol suspendiert und mit 0,22 ml Thioessigsäure versetzt Nach !ständigem Erhitzen am Rückfluß wird analog Beispiel 1 aufgearbeitet Man erhält 0,34 g 17«-(3-Hydroxypropyl)-17^-hydroxy-7a-thioaceiyl-4-androsten-3-on vom Schmelzpunkt 187 -192° C.0.5 g of 17 "- (3-hydroxypropyl) -170-hydroxy-4,6-androstadien-3-one is suspended in 2½ ml of tetrahydrofuran and 1 ml of methanol and mixed with 0.22 ml of thioacetic acid. After constant refluxing is worked up analogously to Example 1. 0.34 g of 17 "- (3-hydroxypropyl) -17 ^ -hydroxy-7a-thioaceiyl-4-androsten-3-one with a melting point of 187-192 ° C. is obtained.

UV:e239 = 18 400.UV: e239 = 18,400.

Beispiel 4Example 4

1 g 17/J-Hydroxy-17Ä-(3-hydroxypropyl)-4,6-androstadien-3-on wird in 8 ml Methanol mit 1 ml Thicpropiontäure 1,5 Stunden unter Rückfluß erhitzt Danach wird im Vakuum eingedampft und der Rückstand aus Aceton-Hexan umkristallisiert Man erhält 0,63 g 17^-Hydroxy-17iX-{3-hydroxypropyl)-7a-propionyltiiio-4-androsten-3-on vom Schmelzpunkt 165— 167°C.1 g of 17 / J-Hydroxy-17Ä- (3-hydroxypropyl) -4,6-androstadien-3-one is refluxed in 8 ml of methanol with 1 ml of thicpropionic acid for 1.5 hours. Thereafter it is evaporated in vacuo and the residue is recrystallized from acetone-hexane. 0.63 g is obtained 17 ^ -Hydroxy-17iX- {3-hydroxypropyl) -7a-propionyltiiio-4-androsten-3-one with a melting point of 165-167 ° C.

Claims (3)

Patentansprüche:Patent claims: 1. Verfahren zur Herstellung von 17a-(3-HydroxypropyI)-17|9-hydroxy-7ii-thioaIkanoyl-4-androsten-3-onen mit bis zu 6 C-Atomen in der Thioalkanoylgruppe, dadurch gekennzeichnet, daß man 17<x-(3-HydroxypropyI)-l 7/?-hydroxy-4,6-androstadien-3-on in einem protisclien Lösungsmittel oder Gemischen davon, gegebenenfalls in Gegenwart eines Lösungsvermittlers, bei Temperaturen von 0° bis zur Siedehitze mit einer Thioalkansäure umsetzt1. Process for the preparation of 17a- (3-hydroxypropyl) -17 | 9-hydroxy-7ii-thioaIkanoyl-4-androsten-3-ones with up to 6 carbon atoms in the thioalkanoyl group, characterized in that one 17 <x- (3-HydroxypropyI) -l 7 /? - hydroxy-4,6-androstadien-3-one in a protic solvent or mixtures thereof, optionally in the presence a solubilizer, at temperatures from 0 ° to boiling point with a thioalkanoic acid implements 2.17<x-(3-Hydroxypropyl)-170-hydroxy-7a-thioacetyI-4-androsten-3-on. 2.17 <x- (3-hydroxypropyl) -170-hydroxy-7a-thioacetyI-4-androsten-3-one. 3.17«-{3-Hydroxypropyl)-l70-hydroxy-7a-thiopropionyM-androsten-3-on. 3.17 "- {3-Hydroxypropyl) -170-hydroxy-7a-thiopropionyM-androsten-3-one.
DE19762609694 1976-03-05 1976-03-05 17 a- (3-Hydroxpropyl) -17 ß-hydroxy-7 a-thioalkanoyl-4-androsten-3-ones and process for their preparation Expired DE2609694C3 (en)

Priority Applications (25)

Application Number Priority Date Filing Date Title
DE19762609694 DE2609694C3 (en) 1976-03-05 1976-03-05 17 a- (3-Hydroxpropyl) -17 ß-hydroxy-7 a-thioalkanoyl-4-androsten-3-ones and process for their preparation
AU22633/77A AU513542B2 (en) 1976-03-05 1977-02-24 A J-keto-steroids
IE451/77A IE44711B1 (en) 1976-03-05 1977-03-02 17 -hydroxypropyl-4-3-keto-steroids and esters thereof, and process for their manufacture
CH261377A CH631462A5 (en) 1976-03-05 1977-03-02 METHOD FOR PRODUCING NEW STEROIDS OF THE ANDROSTANE OR OESTRANE SERIES.
US05/773,982 US4118488A (en) 1976-03-05 1977-03-03 4-Androsten-3-ones and process for the preparation thereof
DD7700197658A DD128659A5 (en) 1976-03-05 1977-03-03 PROCESS FOR THE PREPARATION OF 4-ANDROST-3-ONEN
AT0141377A AT365611B (en) 1976-03-05 1977-03-03 METHOD FOR PRODUCING NEW 17ALPHA- (3-R2-OXYPROPYL) -17BETA-R1-OXY-4-GONEN-ONES
SU772457127A SU755202A3 (en) 1976-03-05 1977-03-03 Method of continuous production of vinyl chloride (co)-polymers
IL51586A IL51586A (en) 1976-03-05 1977-03-03 3-oxo-17 beta-hydroxy-17 alpha-hydroxypropyl androstane and estrane derivatives,process for their preparation and pharmaceutical preparations containing them
LU76883A LU76883A1 (en) 1976-03-05 1977-03-03
CS148077A CS200507B2 (en) 1976-03-05 1977-03-04 Process for preparing 17alpha-/3-r2-oxypropyl/-17beta-r1-oxy-4- genon-3-ones
JP2370377A JPS52111552A (en) 1976-03-05 1977-03-04 44androstenee33one and preparation thereof
NL7702369A NL7702369A (en) 1976-03-05 1977-03-04 4-ANDROSTEEN-3-ONES AND METHOD FOR PREPARING THIS AND METHOD FOR PREPARING A MEDICINAL PRODUCT WITH DIURETIC ACTION.
SE7702455A SE420732B (en) 1976-03-05 1977-03-04 SET TO MAKE 4-GONEN-3-ONER
BE175469A BE852089A (en) 1976-03-05 1977-03-04 ANDROSTENONES AND MEDICINAL PRODUCTS CONTAINING IT
HUSC000597 HU181969B (en) 1976-03-05 1977-03-04 Process for preparing 4-androstan-3-one derivatives
DK96177A DK146856C (en) 1976-03-05 1977-03-04 ANALOGY PROCEDURE FOR THE PREPARATION OF 17ALFA- (3-HYDROXYPROPYL) -17BETA-HYDROXY-4-GONEN-3-ONER
CA273,185A CA1078826A (en) 1976-03-05 1977-03-04 4-androsten-3-one and process for its production
ES456543A ES456543A1 (en) 1976-03-05 1977-03-04 Procedure for the preparation of 4-androsten-3-onas. (Machine-translation by Google Translate, not legally binding)
FR7706567A FR2342990A1 (en) 1976-03-05 1977-03-07 ANDROSTENONES AND MEDICINAL PRODUCTS CONTAINING IT
GB9464/77A GB1579298A (en) 1976-03-05 1977-03-07 17a-hydroxypropyl-4-3-keto-steroids and esters and ethers thereof and process for their manufactgure
CS786764A CS200509B2 (en) 1976-03-05 1978-10-17 Process for preparing 17alpha-/3-r2-oxypropyl/-17beta-r1-oxy-4-gonen-3-ones
AT0180980A AT370110B (en) 1976-03-05 1980-04-02 METHOD FOR PRODUCING NEW 4-ANDROST-3-ONES
CH306781A CH629225A5 (en) 1976-03-05 1981-05-12 Process for the preparation of delta 4-3-ketosteroids
DK403382A DK403382A (en) 1976-03-05 1982-09-09 PROCEDURE FOR THE PREPARATION OF 4-ANDROSTEN-3-ONER

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DE19762609694 DE2609694C3 (en) 1976-03-05 1976-03-05 17 a- (3-Hydroxpropyl) -17 ß-hydroxy-7 a-thioalkanoyl-4-androsten-3-ones and process for their preparation

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DE2609694A1 DE2609694A1 (en) 1977-09-15
DE2609694B2 DE2609694B2 (en) 1977-12-29
DE2609694C3 true DE2609694C3 (en) 1978-08-24

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