DE2609694B2 - 17 ALPHA- (3-HYDROXPROPYL) -17 BETA- HYDROXY-7 ALPHA-THIOALKANOYL-4-ANDROSTEN- 3-ONE AND THE PROCESS FOR THE PREPARATION - Google Patents

17 ALPHA- (3-HYDROXPROPYL) -17 BETA- HYDROXY-7 ALPHA-THIOALKANOYL-4-ANDROSTEN- 3-ONE AND THE PROCESS FOR THE PREPARATION

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Publication number
DE2609694B2
DE2609694B2 DE19762609694 DE2609694A DE2609694B2 DE 2609694 B2 DE2609694 B2 DE 2609694B2 DE 19762609694 DE19762609694 DE 19762609694 DE 2609694 A DE2609694 A DE 2609694A DE 2609694 B2 DE2609694 B2 DE 2609694B2
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Prior art keywords
hydroxy
hydroxypropyl
androsten
alpha
thioalkanoyl
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Granted
Application number
DE19762609694
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German (de)
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DE2609694C3 (en
DE2609694A1 (en
Inventor
Rainer Dr 4619 Bergkamen; Krieger Bernhard Dr 4750 Unna 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 CH261377A priority patent/CH631462A5/en
Priority to IE451/77A priority patent/IE44711B1/en
Priority to US05/773,982 priority patent/US4118488A/en
Priority to IL51586A priority patent/IL51586A/en
Priority to DD7700197658A priority patent/DD128659A5/en
Priority to AT0141377A priority patent/AT365611B/en
Priority to LU76883A priority patent/LU76883A1/xx
Priority to SU772457127A priority patent/SU755202A3/en
Priority to SE7702455A priority patent/SE420732B/en
Priority to NL7702369A priority patent/NL7702369A/en
Priority to DK96177A priority patent/DK146856C/en
Priority to CA273,185A priority patent/CA1078826A/en
Priority to ES456543A priority patent/ES456543A1/en
Priority to HUSC000597 priority patent/HU181969B/en
Priority to BE175469A priority patent/BE852089A/en
Priority to JP2370377A priority patent/JPS52111552A/en
Priority to CS148077A priority patent/CS200507B2/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

2020th

Die Erfindung betrifft 1 7λ-(3-HydroxypropyI)-17/9-hydroxy-7a-thioalkanoyl-4-androsten-3-one und ein Verfahren zu deren Herstellung.The invention relates to 17λ- (3-hydroxypropyl) -17 / 9-hydroxy-7a-thioalkanoyl-4-androsten-3-ones and a method for their production.

Unter der Gruppierung Thioalkanoyl sind solche Gruppen zu verstehen, die sich von niederen Thioalkansäuren mit bis zu 6 C-Atomen, wie z. B. der Thioessig- und der Thiopropionsäure, ableiten.The grouping thioalkanoyl is to be understood as meaning those groups which differ from lower thioalkanoic acids with up to 6 carbon atoms, such as B. the thioacetic and thiopropionic acid derived.

Die erfindungsgemäßen Verbindungen selbst besitzen pharmakologisch wertvolle Eigenschaften, und ω insbesondere ist die 7a-Thioacetylverbindung vorteilhaft als Zwischenprodukt zur Herstellung des bekannten Aldosteronblockers Spironolacton [3-(17/?-Hydroxy-7<x-thioacetyl-3-oxo-4-androsten-17«-yl)-propionsäurelacton] geeignet. J5The compounds according to the invention themselves have pharmacologically valuable properties, and ω in particular, the 7a-thioacetyl compound is advantageous as an intermediate for the preparation of the known Aldosterone blockers Spironolactone [3- (17 /? - Hydroxy-7 <x-thioacetyl-3-oxo-4-androstene-17 «-yl) -propionic acid lactone] suitable. J5

Aus der DT-OS 22 51 476 ist ein Verfahren bekannt, bei dem /?-(3-Keto-17j3-hydroxy-4,6-androstadien-17«- yl)-propionaldehyddialkyl- oder -alkylenacetale mit Thiocarbonsäuren unter Zusatz von Wasser und einem mit Wasser mischbaren organischen Lösungsmittel zu den entsprechenden j3-(3-Keto-7«-thioacetyl-17j9-hydroxy-4-androsien-17«-yl)-propionaldehyddialkyl- oder -alkylenacetalen umgesetzt werden, die dann in saurer Lösung zu den ,8-(3-Keto-7*-thioacetyI-17^-hydroxy-4-androsten-17a-yl)-propionsäure-y-lactonen oxydiert 41J werden.From DT-OS 22 51 476 a process is known in which /? - (3-keto-17j3-hydroxy-4,6-androstadien-17 "- yl) propionaldehyde dialkyl or alkylene acetals with thiocarboxylic acids with the addition of water and a water-miscible organic solvent to give the corresponding j3- (3-keto-7'-thioacetyl-17j9-hydroxy-4-androsien-17'-yl) propionaldehyde dialkyl or alkylene acetals, which are then converted into acidic solution to, 8- (3-keto-7 * -thioacetyI-17 ^ -hydroxy-4-androsten-17a-yl) propionic acid-y-lactones oxidized 4 1 J are.

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

Des weiteren liegen die mit dem erfindungsgemäßen Verfahren erhaltenen Gesamtausbeuten an Spironolacton deutlich über den Ausbeuten, die mit dem bekannten Verfahren erhalten werden.Furthermore, the total yields of spironolactone 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-Hydroxypropyl)-17j3-hydroxy-4,6-androstadien-3-on in einem proti- γ-, sehen Lösungsmittel oder Gemischen davon gegebenenfalls in Gegenwart eines Lösungsvermittlers bei Temperaturen von 0° bis zur Siedehitze mit einer Thioalkansäure leicht umsetzen kann.It has now been found that 17 "- (3-hydroxypropyl) -17j3-hydroxy-4,6-androstadien-3-one in a proti- γ-, see solvent or mixtures thereof, optionally in the presence of a solubilizer at temperatures of 0 ° can easily react with a thioalkanoic acid up to boiling point.

Der Verlauf der erfindungsgemäßen Reaktion ist wi durchaus überraschend, da zu erwarten gewesen wäre, daß auch gleichzeitig eine Esterbildung am Kohlenstoffatom C —23 auftritt. Führt man nämlich die Thioacetyüerur.g unter den Bedingungen, der DTPS !!21610 durch, so erhält man überwiegend das C — 23 acetylierte ι,ί Produkt, wie folgendes Beispiel zeigt:The course of the reaction according to the invention is wi Quite surprising, since it would have been expected that ester formation at the carbon atom would also occur at the same time C-23 occurs. If one leads namely the Thioacetyüerur.g under the conditions of DTPS !! 21610 through, one obtains predominantly the C - 23 acetylated ι, ί Product, as the following example shows:

2 g 17a-(3-Hydroxypropyl)-17j3-hydroxy-4,6-androstadien-3-on werden in 1,8 ml Thioessigsäure 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)-170-hydroxy-7«-thioacetyl-4-androsten-3-on erhalten.2 g of 17a- (3-hydroxypropyl) -17j3-hydroxy-4,6-androstadien-3-one are heated in 1.8 ml of thioacetic acid at 90 ° C. for 30 minutes. The excess thioacetic acid is then removed by distillation under reduced pressure and the residue is chromatographed. 1.1 g of 17 "- {3-acetoxypropyI) -170-hydroxy-7" -thioacetyl-4-androsten-3-one are obtained.

Das für das erfindungsgemäße Verfahren verwendete Ausgangsmaterial 17«-(3- Hydroxypropyl)-17/i-hydroxy-4,6-androstadien-3-on kann nach an sich bekannten Methoden aus 17«-(3-Hydroxypropyl)-17/M1ydroxy-4-androsten-3-on, z. B. durch Dehydrierung mit Chloranil hergestellt werden (US-PS 31 37 690).The starting material 17 "- (3-hydroxypropyl) -17 / i-hydroxy-4,6-androstadien-3-one used for the process according to the invention can be prepared from 17" - (3-hydroxypropyl) -17 / M 1y droxy-4-androsten-3-one, e.g. B. be prepared by dehydration with chloranil (US-PS 31 37 690).

Zur Durchführung des erfindungsgemäßen Verfahrens wird das !7a-(3-Hydroxypropyl)-17/?-hydroxy-4,6-androstadien in einem protischen Lösungsmittel gelöst, wobei auch inerte Lösungsmittel zugesetzt werden können.To carry out the process according to the invention, 7a- (3-hydroxypropyl) -17 /? - hydroxy-4,6-androstadiene is used dissolved in a protic solvent, inert solvents also being added can.

Als protische Lösungsmittel seien insbes· idere genannt niedere Alkenole wie Methanol, Äthanol und Butanol, cyclische Äther wie Tetrahydrofuran und Dioxan, niedere Ketone wie Aceton und Säurederivate wie Dimethylformamid. Es können aber auch Gemische dieser Lösungsmittel untereinander eingesetzt werden. Der Zusatz von inerten Lösungsmittel, die als Lösungsvermittler dienen, wie z. B. Heptan, Benzol und Diisopropyläther, stört den erfindungsgemäßen Reaktionsverlauf nicht.Protic solvents are particularly suitable called lower alkenols such as methanol, ethanol and butanol, cyclic ethers such as tetrahydrofuran and Dioxane, lower ketones such as acetone and acid derivatives such as dimethylformamide. But mixtures can also be used 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, interferes with the course of the reaction according to the invention not.

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

Die Reakt'on läuft an sich schon bei Temperaturen unterhalb Raumtemperatur ab. Es ist jedoch vorteilhaft, das Reaktionsgemisch zu erwärmen. Bei Temperaturen im Bereich des Siedepunktes ist die Reaktion bereits nach einer Stunde beendet.The reaction takes place even at temperatures below room temperature. However, it is beneficial to warm the reaction mixture. At temperatures in the range of the boiling point, the reaction is already finished after an hour.

Das Reaktionsprodukt wird nach an sich bekannten Methoden wie Filtration abgetrennt und beispielsweise durch Chromatographie und/oder Umkristallisation gereinigt.The 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 17a-(3-Hydroxypropyl)-17j?-hydroxy-7a-thioacetyl-4-androsten-3-on als Zwischenprodukt zur Herstellung des bekannten Spironolactons geeignet. Hierzu wird das 17a-(3-HydroxypropyI)-17/?-hydroxy-7a-thioacetyl-4-androsten-3-on nach an sich bekannten Methoden mit Chromsäure unter Lactonisierung zum Spironolacton oxydiert, wofür das folgende Beispiel steht:In particular, the compound according to the invention is 17a- (3-hydroxypropyl) -17j? -Hydroxy-7a-thioacetyl-4-androsten-3-one suitable as an intermediate for the production of the well-known spironolactone. For this purpose, the 17a- (3-hydroxypropyl) -17 /? - hydroxy-7a-thioacetyl-4-androsten-3-one according to methods known per se with chromic acid with lactonization to give spironolactone oxidizes, as the following example stands for:

0,5 g 17«-(3-Hydroxypropyl)-17j9-hydroxy-7«-thioacetyl-4-androsten-3-on werden bei 00C in 10 ml Aceton suspendiert. Zu dieser Suspension läßt man langsam 0,52 ml Jones-Reagens zutropfen, so daß die Temperatur 5° C nicht überschreitet. Man rührt 1 Stunde bei 0-50C. Das überschüssige Jones-Reagens wird mit Methanol zerstört, die ausgefallenen Chromsalze abfiltriert, das Filtrat zur Trockne eingeengt und durch Zugabe von Methanol kristallisiert. Nach Absaugen und Trocknen erhält man 0,38 g 3-(17/?-Hydroxy-7«-thioacetyl-3-oxo-4-androsten-17a-y!)-propionsäurelacton vom Schmelzpunkt 202 - 205° C.0.5 g of 17 "- (3-hydroxypropyl) -17j9-hydroxy-7" -thioacetyl-4-androstene-3-one are suspended at 0 0 C in 10 ml of acetone. 0.52 ml of Jones reagent is slowly added dropwise to this suspension so that the temperature does not exceed 5.degree. The mixture is stirred for 1 hour at 0-5 0 C. The excess Jones reagent is destroyed with methanol, the precipitated chromium salts filtered off, the filtrate was concentrated to dryness and crystallized by addition of methanol. After filtering off with suction and drying, 0.38 g of 3- (17 /? - Hydroxy-7 «-thioacetyl-3-oxo-4-androstene-17a-y!) -Propionic acid lactone with a melting point of 202-205 ° C. is obtained.

Die nachfolgenden Beispiele sollen das erfindungsgemäße Verfahren erläutern.The following examples are intended to explain the process according to the invention.

Beispiel 1example 1

1 g 17«-(3-Hydroxypropyl)-17/?-hydroxy-4,6-androstadien-3-on wird in 5 ml Methanol gelöst. Zu dieser Lösung werden in der Wärme 0,43 ml Thioessigsäure1 g of 17 "- (3-hydroxypropyl) -17 /? - hydroxy-4,6-androstadien-3-one is dissolved in 5 ml of methanol. 0.43 ml of thioacetic acid are added to this solution when hot

sisi

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)-17/?-hydroxy-7ft-thioacetyl-4-androsten-3-on vom Schmelzpunkt 187-192° C.
UV: E239 = 18400.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) -17 /? - hydroxy-7ft-thioacetyl-4-androsten-3-one with a melting point of 187-192 ° C. are obtained.
UV: E239 = 18400.

Beispiel 2Example 2

3 g 17«-(3-Hydroxypropyl)-17/J-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 i. Man erhält 2,4 g 17a-(3-Hydroxypropyl)-17/i-hydroxy-7*- thioacetyl-4-androsten-3-on vom Schmelzpunkt 187-192°C3 g of 17 "- (3-hydroxypropyl) -17 / J-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 i. Man receives 2.4 g of 17a- (3-hydroxypropyl) -17 / i-hydroxy-7 * - thioacetyl-4-androsten-3-one with a melting point of 187-192 ° C

UV: £239 = 18 400.UV: £ 239 = 18,400.

Beispiel 3Example 3

0,5 g 17«-(3-Hydroxypropyl)-17ß-hydroxy-4,6-androstadien-3-on wird in 2,5 ml Tetrahydrofuran und 1 ml Methanol suspendiert und mit 0,22 ml Thioessigsäure versetzt. Nach 1 stündigem Erhitzen am Rückfluß wird analog Beispiel 1 aufgearbeitet. Man erhält 0,34 g 17Ä-(3-Hydroxypropyl)-17ß-hydroxy-7«-thioacetyl-4-androsten-3-on vom Schmelzpunkt 187 — 192°C. ίο UV:e239 = 18 400.0.5 g of 17 "- (3-hydroxypropyl) -17β-hydroxy-4,6-androstadien-3-one is suspended in 2.5 ml of tetrahydrofuran and 1 ml of methanol, and 0.22 ml of thioacetic acid is added. After refluxing for 1 hour, work-up is carried out analogously to Example 1. 0.34 g of 17 [3-hydroxypropyl) -17 [beta] -hydroxy-7 [deg.] -Thioacetyl-4-androsten-3-one with a melting point of 187-192 ° C. is obtained. ίο UV: e 2 39 = 18 400.

Beispiel 4Example 4

1 g 17j3-Hydroxy-17«-(3-hydroxypropyl)-4,6-androstadien-3-on wird in 8 ml Methanol mit 1 ml Thiopropionsäure 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- 17«-(3-hydroxypropyl)-7<x-propionylthio-4-androsten-3-on vom Schmelzpunkt 165— 167" C.1 g of 17j3-hydroxy-17 "- (3-hydroxypropyl) -4,6-androstadien-3-one is refluxed in 8 ml of methanol with 1 ml of thiopropionic acid for 1.5 hours. Thereafter is evaporated in vacuo and the residue is recrystallized from acetone-hexane. 0.63 g is obtained 17 /? - Hydroxy-17 "- (3-hydroxypropyl) -7 <x-propionylthio-4-androsten-3-one from melting point 165-167 "C.

Claims (3)

Patentansprüche:Patent claims: 1. Verfahren zur Hersteilung von 17a-(3-Hydroxypropyl)-17ß-hydroxy-7«-thioalkanoy l-4-androsten- r> 3-onen mit Ibis zu 6 C-Atomen in der Thioalkanoylgruppe, dadurch gekennzeichnet, daß man 17a(3-Hydroxypropyl)-170-hydroxy-4,6-androstadien-3-on in einem protischen Lösungsmittel oder Gemischen davon, gegebenenfalls in Gegenwart eines Lösungsvermittlers, bei Temperaturen von 0° bis zur Siedehitze mit einer Thioalkansäure umsetzt.
2.17a-(3-Hydroxypropyl)-17jS-hydroxy-7iX-thio-1. A process for the preparation of 17a- (3-hydroxypropyl) -17ß-hydroxy-7 "-thioalkanoy l-4-androsten- r > 3-ones with ibis to 6 carbon atoms in the thioalkanoyl group, characterized in that 17a (3-Hydroxypropyl) -170-hydroxy-4,6-androstadien-3-one in a protic solvent or mixtures thereof, optionally in the presence of a solubilizer, at temperatures from 0 ° to boiling point with a thioalkanoic acid.
2.17a- (3-hydroxypropyl) -17jS-hydroxy-7iX-thio- acetyl-4-androsten-3-on.acetyl-4-androsten-3-one. 3.17a-(3-Hydroxypropyl)-17^-hydroxy-7Ä-thiopropionyl-4-androsten-3-on. 3.17a- (3-hydroxypropyl) -17 ^ -hydroxy-7A-thiopropionyl-4-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
CH261377A CH631462A5 (en) 1976-03-05 1977-03-02 METHOD FOR PRODUCING NEW STEROIDS OF THE ANDROSTANE OR OESTRANE SERIES.
IE451/77A IE44711B1 (en) 1976-03-05 1977-03-02 17 -hydroxypropyl-4-3-keto-steroids and esters thereof, and process for their manufacture
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
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
LU76883A LU76883A1 (en) 1976-03-05 1977-03-03
SU772457127A SU755202A3 (en) 1976-03-05 1977-03-03 Method of continuous production of vinyl chloride (co)-polymers
US05/773,982 US4118488A (en) 1976-03-05 1977-03-03 4-Androsten-3-ones and process for the preparation thereof
CA273,185A CA1078826A (en) 1976-03-05 1977-03-04 4-androsten-3-one and process for its production
DK96177A DK146856C (en) 1976-03-05 1977-03-04 ANALOGY PROCEDURE FOR THE PREPARATION OF 17ALFA- (3-HYDROXYPROPYL) -17BETA-HYDROXY-4-GONEN-3-ONER
SE7702455A SE420732B (en) 1976-03-05 1977-03-04 SET TO MAKE 4-GONEN-3-ONER
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)
HUSC000597 HU181969B (en) 1976-03-05 1977-03-04 Process for preparing 4-androstan-3-one derivatives
BE175469A BE852089A (en) 1976-03-05 1977-03-04 ANDROSTENONES AND MEDICINAL PRODUCTS CONTAINING IT
JP2370377A JPS52111552A (en) 1976-03-05 1977-03-04 44androstenee33one and preparation thereof
CS148077A CS200507B2 (en) 1976-03-05 1977-03-04 Process for preparing 17alpha-/3-r2-oxypropyl/-17beta-r1-oxy-4- genon-3-ones
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.
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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DE2609694B2 true DE2609694B2 (en) 1977-12-29
DE2609694C3 DE2609694C3 (en) 1978-08-24

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