DD242231A5 - 13-ALKYL-17 BETA (3-ACYLOXY-PROPYL) GONANES - Google Patents
13-ALKYL-17 BETA (3-ACYLOXY-PROPYL) GONANES Download PDFInfo
- Publication number
- DD242231A5 DD242231A5 DD85284398A DD28439885A DD242231A5 DD 242231 A5 DD242231 A5 DD 242231A5 DD 85284398 A DD85284398 A DD 85284398A DD 28439885 A DD28439885 A DD 28439885A DD 242231 A5 DD242231 A5 DD 242231A5
- Authority
- DD
- German Democratic Republic
- Prior art keywords
- alkyl
- gonadien
- hydroxy
- gonanes
- propyl
- Prior art date
Links
Classifications
-
- 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
- C07J41/0077—Normal steroids containing one or more nitrogen atoms not belonging to a hetero ring not covered by C07J41/0005 substituted in position 11-beta by a carbon atom, further substituted by a group comprising at least one further carbon atom
- C07J41/0083—Normal steroids containing one or more nitrogen atoms not belonging to a hetero ring not covered by C07J41/0005 substituted in position 11-beta by a carbon atom, further substituted by a group comprising at least one further carbon atom substituted in position 11-beta by an optionally substituted phenyl group not further condensed with other rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Steroid Compounds (AREA)
- Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Medicines Containing Material From Animals Or Micro-Organisms (AREA)
Abstract
Description
mit einem Säurechlorid oder Säureanhydrid der allgemeinen Formel III bzw. Formel IV 0with an acid chloride or acid anhydride of the general formula III or formula IV 0
R-C-ClR-C-Cl
• ,(III)•, (III)
IlIl
(R-C)2O(RC) 2 O
(IV)(IV)
R die oben angegebene Bedeutung hat, in Gegenwart von Basen bei Temperaturen zwischen O und 60°C umsetzt und gegebenenfalls anschließend mit Hydroxylamin-hydrochlorid in Gegenwart von tertiären Aminen bei Temperaturen zwischen -20 und +4O0C umsetzt.R has the abovementioned meaning, in the presence of bases at temperatures between 0 and 60 ° C and optionally then reacted with hydroxylamine hydrochloride in the presence of tertiary amines at temperatures between -20 and + 4O 0 C.
Die Erfindung betrifft ein Verfahren zur Herstellung von neuen 13—Alkyl-17ß-(3-acyloxypropyl)-gonanen der allgemeinen Formel I sowie diese Verbindungen enthaltende pharmazeutische Präparate.The invention relates to a process for the preparation of novel 13-alkyl-17ß- (3-acyloxypropyl) -gonanen of the general formula I as well as these compounds containing pharmaceutical preparations.
Charakteristik der bekannten technischen LösungenCharacteristic of the known technical solutions
13a-Alkyl-17ß-(3-hydroxypropyl)-4,9-gonadien-3-one sind aus der europäischen Patentanmeldung Nr.84730062.1 bekannt. Diese Verbindungen besitzen eine starke Affinität zum Gestagenrezeptor, ohne selbst gestagene Aktivität zu besitzen. Sie sind kompetitive Antagonisten des Progesterons (Anti-Gestagene) und sind zur Auslösung von Aborten geeignet, da sie das zur Aufrechterhaltung der Schwangerschaft erforderliche Progesteron vom Rezeptor verdrängen. Die Verbindungen sind deshalb wertvoll und interessant im Hinblick auf ihre Verwendung zur postcoitalen (p.c.) Fertilitätskontrolle.13a-Alkyl-17β- (3-hydroxypropyl) -4,9-gonadiene-3-ones are known from European Patent Application No. 84730062.1. These compounds have a strong affinity for the progestagen receptor without self gestagenic activity. They are competitive antagonists of progesterone (anti-progagens) and are suitable for triggering abortions as they displace the progesterone required to maintain pregnancy from the receptor. The compounds are therefore valuable and interesting in their use for postcoital (p.c.) fertility control.
Ziel der ErfindungObject of the invention
Ziel der Erfindung ist die Bereitstellung neuer Verbindungen gleicher Wirkungsrichtung mit besserer Bioverfügbarkeit, verstärkter Wirkung und längerer Wirkungsdauer.The aim of the invention is the provision of new compounds of the same direction of action with better bioavailability, enhanced effect and longer duration of action.
Darlegung des Wesens der ErfindungExplanation of the essence of the invention
Der Erfindung liegt die Aufgabe zugrunde, neue Verbindungen mit den gewünschten Eigenschaften und Verfahren zu ihrerThe invention has for its object to provide novel compounds with the desired properties and methods for their
Herstellung aufzufinden.To find production.
Erfindungsgemäß werden neue 13a-Alkylgonane der allgemeinen Formel IAccording to the invention, new 13a-alkylgonanes of the general formula I
CH2-CH2-CH2-ORCH 2 -CH 2 -CH 2 -OR
(I)(I)
hergestellt, worin R für einen Acylrest mit bis zu 10C-Atomen und X für ein Sauerstoffatom oder die Gruppierung N ~ OHwherein R is an acyl radical having up to 10C atoms and X is an oxygen atom or the grouping N ~ OH
stehen.Es wurde nun gefunden, daß durch Überführung dieser Verbindungen in die 13a-Alkyl-17ß-(3-acyloxypropyl)-gonane der allgemeinen Formel I überraschenderweise ihre Bioverfügbarkeit wesentlich verbessert werden kann. Sie weisen daher bei gleicher oder verstärkter Wirkung eine wesentlich verlängerte Wirkungsdauer im Vergleich zu den vorbekannten 13a-Alkyl-17ß-(3-hydroxypropyi)-4,9-gonadien-3-onen auf. Als weiterer Vorteil stellte sich heraus, daß die neuen Verbindungen ausgezeichnete Kristallisationseigenschaften besitzen. Die Herstellung reiner Wirksubstanzen bereitet daher bei ihnen sehr viel weniger Schwierigkeiten als im Falle der 13a-Alkyl-17ß-(3-hydroxypropyl)-4,9-gonadien-3-one.It has now been found that, surprisingly, their bioavailability can be substantially improved by converting these compounds into the 13a-alkyl-17β- (3-acyloxypropyl) -gonanes of the general formula I. They therefore have the same or enhanced effect a significantly prolonged duration of action in comparison to the previously known 13a-alkyl-17ß- (3-hydroxypropyl) -4,9-gonadiene-3-ones. As a further advantage, it has been found that the novel compounds have excellent crystallization properties. The preparation of pure active substances therefore presents much less difficulty for them than in the case of the 13a-alkyl-17β- (3-hydroxypropyl) -4,9-gonadiene-3-ones.
Weiterhin besitzen sie eine ausgezeichnete chemische Stabilität. Man kann sie problemlos bei Raumtemperatur über einenFurthermore, they have excellent chemical stability. You can easily do it at room temperature over a
größeren Zeitraum ohne Zersetzung lagern.'store longer periods without decomposition. '
Der Acylrest R der allgemeinen Formel I soll bis zu 10 C-Atomen enthalten. Als Acylreste kommen beispielsweise in Frage der Formyl-, Acetyl-, Propionyl-, Butyryl-, Isobutyryl-, Valeryl-, Isovaleryl-, Glycoloyl-, Cyclopentylacetyl-, Mono-, Di-,Trichloracetyl-, Benzoyl-, Trifluormethylbenzoyl- und Nicotinoylrest; bevorzugt sind der Acetyl- und der Benzoylrest.The acyl radical R of the general formula I should contain up to 10 C atoms. Suitable acyl radicals are, for example, the formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, glycoloyl, cyclopentylacetyl, mono-, di-, trichloroacetyl, benzoyl, trifluoromethylbenzoyl and nicotinoyl radical ; preferred are the acetyl and the benzoyl radical.
X steht für ein Sauerstoffatom oder die Gruppierung N ~ OH, wobei der Hydroxyimino-Rest syri- oder antiständig sein kann.X represents an oxygen atom or the group N ~ OH, where the hydroxyimino radical can be syri- or antistatic.
Die Herstellung der erfindungsgemäßen Verbindungen der allgemeinen Formel I erfolgt derart, daß man eine Verbindung derThe compounds of general formula I according to the invention are prepared in such a way that a compound of
Formel IlFormula Il
CH2-CH2-CH2-OHCH 2 -CH 2 -CH 2 -OH
(II)(II)
mit einem Säurechlorid oder Säiirfianhvrlrirl der allnwith an acid chloride or acidifier of the alln
Fnrmpl III h7w Fnrmcl IVFnrmpl III h7w Fnrmcl IV
R-C-Cl (III)R-C-Cl (III)
IlIl
(R-C)2O - (IV),(RC) 2 O - (IV),
R die oben angegebene Bedeutung hat, in Gegenwart von Basen bei Temperaturen zwischen O und 6O0C umsetzt und gegebenenfalls anschließend mit Hydroxylamin-hydrochlorid in Gegenwart von tertiären Aminen bei Temperaturen zwischen -20 und+400C umsetzt.R has the abovementioned meaning, in the presence of bases at temperatures between 0 and 6O 0 C and optionally then reacted with hydroxylamine hydrochloride in the presence of tertiary amines at temperatures between -20 and + 40 0 C.
Die bevorzugten Basen bei der Veresterung sind tertiäre Amine wie beispielsweise Pyridin. Das bevorzugte tertiäre Ami η bei der Umsetzung zur Herstellung der Oxime ist Pyridin.The preferred bases in the esterification are tertiary amines such as pyridine. The preferred tertiary amine in the reaction to produce the oximes is pyridine.
Weitere geeignete tertiäre Basen sind beispielsweise Trimethylamin,Triäthylamin, Ν,Ν-Dimethylaminopyridin, 1,5-Diazabicyclo[4.3.0]nonen-5(DBN) und 1,5-Diazabicyclo[5.4.0]-undecen-5(DBU).Further suitable tertiary bases are, for example, trimethylamine, triethylamine, Ν, Ν-dimethylaminopyridine, 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) and 1,5-diazabicyclo [5.4.0] undecene-5 (DBU) ,
Geeignete Verbindungen der allgemeinen Formel I sind beispielsweise die folgenden:Suitable compounds of the general formula I are, for example, the following:
17ß-(3-Acetoxypropyl)-11ß-(4-dimethylaminophenyl)-17a-hydroxy-13a-methyl-4,9-gonadien-3-on; 17ß-(3-Benzoyloxypropyl)-11ß-(4-dimethylaminophenyl)-17a-hydroxy-13a-methyl-4,9-gonadien-3-on; 17ß-(3-Acetoxypropyl)-11ß-(4-dimethylaminophenyl)-17a-hydroxy-13a-methyl-4,9-gonadien-3-on-anti-oxim.17ß- (3-acetoxypropyl) -11ß- (4-dimethylaminophenyl) -17a-hydroxy-13a-methyl-4,9-gonadien-3-one; 17ß- (3-benzoyloxypropyl) -11ß- (4-dimethylaminophenyl) -17a-hydroxy-13a-methyl-4,9-gonadien-3-one; 17ß- (3-acetoxypropyl) -11ß- (4-dimethylaminophenyl) -17a-hydroxy-13a-methyl-4,9-gonadien-3-one anti-oxime.
Die 13a-A!ky !gonane der al I gemein en Formel I können in Form pharmazeutischer Präparate Verwendung finden. Die Herstellung der Präparate erfolgt nach an sich bekannten Methoden der Galenik durch Mischen mit organischem oder anorganischem inerten Trägermaterial, welches für die enterale, perkutane oder parenterale Applikation geeignet ist.The 13a-A! Ky! Gonanes of the general formula I can be used in the form of pharmaceutical preparations. The preparation of the preparations is carried out according to known methods of galenics by mixing with organic or inorganic inert carrier material, which is suitable for enteral, percutaneous or parenteral administration.
Die Dosierung der erfindungsgemäßen Wirkstoffe liegt beim Menschen bei etwa 10 bis 1 000 mg pro Tag.The dosage of the active compounds according to the invention in humans is about 10 to 1,000 mg per day.
Ausführungsbeispie!Ausführungsbeispie!
Die Erfindung soll an Hand der nachfolgenden Beispiele erläutert werden, ohne sie allerdings darauf zu begrenzen.The invention will be explained with reference to the following examples, without, however, limiting it thereto.
Eine Lösung von 2,4g 11ß-(4-Dimethylaminophenyl)-17a-hydroxy-13a-methyl-17ß-(3-hydroxypropyl)-4,9-gonadien-3-on in 7 ml Pyridin und 14ml Acetanhydrid wird 14 Stunden bei 25°C gerührt. Anschließend gießt man in ca. 5O0C warmes Wasser (100 ml), rührt 15 Minuten und extrahiert die erkaltete Emulsion mit Methylenchlorid. Die Methylenchlorid-Phase wird mit NaHCO3-Lösung neutral gewaschen, über Na2SO4 getrocknet und eingeengt. Kristallisation des Rohprodukts aus Ethylacetat/ Diisopropylether ergibt 2,24g 17ß-(3-Acetoxypropyl)-11ß-(4-dimethylaminophenyl)-17a-hydroxy-13a-methyl-4,9-gonadien-3-on vom Schmelzpunkt 162-164°CA solution of 2.4 g of 11β- (4-dimethylaminophenyl) -17a-hydroxy-13a-methyl-17β- (3-hydroxypropyl) -4,9-gonadien-3-one in 7 ml of pyridine and 14 ml of acetic anhydride is added for 14 hours 25 ° C stirred. Then it is poured into about 5O 0 C warm water (100 ml), stirred for 15 minutes and extracted the cooled emulsion with methylene chloride. The methylene chloride phase is washed neutral with NaHCO 3 solution, dried over Na 2 SO 4 and concentrated. Crystallization of the crude product from ethyl acetate / diisopropyl ether gives 2.24 g of 17β- (3-acetoxy-propyl) -11β- (4-dimethylaminophenyl) -17a-hydroxy-13a-methyl-4,9-gonadien-3-one, m.p. 162-164 ° C
[a]g5 +436,50C (CHCI3, c = 0,515).[a] g 5 +436.5 0 C (CHCl 3 , c = 0.515).
Zu einer Lösung von 700mg 11ß-(4-Dimethylaminophenyl)-17a-hydroxy-13a-methyl-17ß-(3-hydroxypropyl)-4,9-gonadien-3-on in 5ml Pyridin tropft man unter Eiswasserkühlung 0,36ml Benzoylchlorid in 4ml Methylenchlorid. Man rührt 60 Minuten bei +50C, gießt dann in gesättigte NaHCO3-Lösung und extrahiert mit Ethyiacetat. Kristallisation des Rohprodukts aus Hexan/ Diisopropylether ergibt 630mg 17ß-(3-Benzoyloxypropyl)-11ß-(4-dimethylaminophenyl)-17a-hydroxy-13a-methyl-4,9-gonadien-3-on vom Schmelzpunkt 114-116°C.To a solution of 700 mg of 11ß- (4-dimethylaminophenyl) -17a-hydroxy-13a-methyl-17ß- (3-hydroxypropyl) -4,9-gonadien-3-one in 5 ml of pyridine is added dropwise with ice-cooling 0.36 ml of benzoyl chloride in 4 ml of methylene chloride. The mixture is stirred for 60 minutes at +5 0 C, then poured into saturated NaHCO 3 solution and extracted with Ethyiacetat. Crystallization of the crude product from hexane / diisopropyl ether gives 630 mg of 17β- (3-benzoyloxypropyl) -11β- (4-dimethylaminophenyl) -17a-hydroxy-13a-methyl-4,9-gonadien-3-one of melting point 114-116 ° C.
Eine Lösung von 630mg 17ß-(3-Acetoxypropyl)-11ß-(4-dimethylaminophenyl)-17a-hydroxy-13a-methyl-4,9-gonadien-3-on in 10ml Pyridin wird nach Zusatz von 600mg Hydroxylamin-hydrochlorid 1,5 Stunden bei 00C gerührt. Anschließend gießt man in Eiswasser/gesättigte NH4CI-Lösung und extrahiert mit Ethylacetat. Nach Chromatographie an Kieselgel mit Hexan/Ethylacetat erhält man 410 mg 17ß-(3-Acetoxypropyl)-11ß-(4-dimethylaminophenyl)-17a-hydroxy-13a-methyl-4,9-gonadien-3-on-anti-oxim vom Schmelzpunkt 201-2040CA solution of 630 mg of 17β- (3-acetoxypropyl) -11β- (4-dimethylaminophenyl) -17a-hydroxy-13a-methyl-4,9-gonadien-3-one in 10 ml of pyridine is added after addition of 600 mg of hydroxylamine hydrochloride 1, Stirred at 0 0 C for 5 hours. It is then poured into ice-water / saturated NH 4 Cl solution and extracted with ethyl acetate. Chromatography on silica gel with hexane / ethyl acetate gives 410 mg of 17β- (3-acetoxypropyl) -11β- (4-dimethylaminophenyl) -17a-hydroxy-13a-methyl-4,9-gonadien-3-one anti-oxime of Melting point 201-204 0 C
UV (MeOH): Amax288nm (ε = 27400).UV (MeOH): A max 288nm (ε = 27400).
Zusammensetzung einerTablette mit 10mg 17ß-(3-Acetoxy-propyl)-11ß-(4-n,n-dimethylamino)-phenyl)-17a-hydroxy-13amethyl-4,9-gonadien-3-on zur oralen ApplikationComposition of a tablet containing 10mg of 17β- (3-acetoxy-propyl) -11β- (4-n, n-dimethylamino) -phenyl) -17a-hydroxy-13amethyl-4,9-gonadien-3-one for oral administration
10 mg 17ß-(3-Acetoxypropyl)-11ß-((4-n,n-dimethylamino)-phenyl)-17a-hydroxy-13a-methyl-4,9-gonadien-3-on 140,5mg Laktose 69,5mg Maisstärke10 mg of 17β- (3-acetoxypropyl) -11β - ((4-n, n-dimethylamino) -phenyl) -17a-hydroxy-13a-methyl-4,9-gonadien-3-one 140.5 mg lactose 69.5 mg corn starch
2,5mg Polyvinylpyrrolidon 252.5 mg polyvinylpyrrolidone 25
2,0 mg Aerosil2.0 mg Aerosil
0,5mg Magnesiumstearat 225,0 mg' 0.5 mg magnesium stearate 225.0 mg '
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19843446661 DE3446661A1 (en) | 1984-12-18 | 1984-12-18 | NEW 13 (ALPHA) -ALKYL-17 (BETA) - (3-ACYLOXYPROPYL) GONANA |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DD242231A5 true DD242231A5 (en) | 1987-01-21 |
Family
ID=6253403
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DD85284398A DD242231A5 (en) | 1984-12-18 | 1985-12-16 | 13-ALKYL-17 BETA (3-ACYLOXY-PROPYL) GONANES |
Country Status (17)
| Country | Link |
|---|---|
| EP (1) | EP0186834B1 (en) |
| JP (1) | JPH0662665B2 (en) |
| AT (1) | ATE45957T1 (en) |
| AU (1) | AU580646B2 (en) |
| CA (1) | CA1262894A (en) |
| DD (1) | DD242231A5 (en) |
| DE (2) | DE3446661A1 (en) |
| DK (1) | DK166502B1 (en) |
| ES (1) | ES8701194A1 (en) |
| FI (1) | FI83089C (en) |
| GR (1) | GR853017B (en) |
| HU (1) | HU193357B (en) |
| IE (1) | IE58147B1 (en) |
| NO (1) | NO163014C (en) |
| NZ (1) | NZ214449A (en) |
| PT (1) | PT81690B (en) |
| ZA (1) | ZA859666B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4434488A1 (en) | 1994-09-14 | 1996-03-21 | Schering Ag | Steroid esters and amides, processes for their preparation and their pharmaceutical use |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA8231B (en) * | 1981-01-09 | 1982-11-24 | Roussel Uclaf | New 11 -substituted steroid derivatives, their preparation, their use as medicaments, the compositions containing them and the new intermediates thus obtained |
| EP0116974B1 (en) * | 1983-02-18 | 1986-10-29 | Schering Aktiengesellschaft | 11-beta-aryl-estradienes, process for their preparation and pharmaceutical compositions containing them |
| ES533260A0 (en) * | 1983-06-15 | 1985-02-01 | Schering Ag | PROCEDURE FOR THE PREPARATION OF 13A-ALQUILGONANOS |
-
1984
- 1984-12-18 DE DE19843446661 patent/DE3446661A1/en not_active Withdrawn
-
1985
- 1985-12-03 FI FI854788A patent/FI83089C/en not_active IP Right Cessation
- 1985-12-05 NZ NZ214449A patent/NZ214449A/en unknown
- 1985-12-13 AT AT85115925T patent/ATE45957T1/en not_active IP Right Cessation
- 1985-12-13 DE DE8585115925T patent/DE3572670D1/en not_active Expired
- 1985-12-13 EP EP85115925A patent/EP0186834B1/en not_active Expired
- 1985-12-16 IE IE316985A patent/IE58147B1/en not_active IP Right Cessation
- 1985-12-16 DD DD85284398A patent/DD242231A5/en not_active IP Right Cessation
- 1985-12-16 ES ES549998A patent/ES8701194A1/en not_active Expired
- 1985-12-16 GR GR853017A patent/GR853017B/el unknown
- 1985-12-17 JP JP60282175A patent/JPH0662665B2/en not_active Expired - Lifetime
- 1985-12-17 DK DK587585A patent/DK166502B1/en not_active IP Right Cessation
- 1985-12-17 CA CA000497807A patent/CA1262894A/en not_active Expired
- 1985-12-17 HU HU854813A patent/HU193357B/en not_active IP Right Cessation
- 1985-12-17 NO NO855090A patent/NO163014C/en unknown
- 1985-12-17 PT PT81690A patent/PT81690B/en not_active IP Right Cessation
- 1985-12-18 AU AU51436/85A patent/AU580646B2/en not_active Ceased
- 1985-12-18 ZA ZA859666A patent/ZA859666B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| GR853017B (en) | 1986-04-15 |
| AU5143685A (en) | 1986-06-26 |
| DE3446661A1 (en) | 1986-06-19 |
| AU580646B2 (en) | 1989-01-19 |
| JPS61145197A (en) | 1986-07-02 |
| ES549998A0 (en) | 1986-12-01 |
| DK587585A (en) | 1986-06-19 |
| PT81690A (en) | 1986-01-01 |
| ATE45957T1 (en) | 1989-09-15 |
| IE853169L (en) | 1986-06-18 |
| FI854788A0 (en) | 1985-12-03 |
| FI83089C (en) | 1991-05-27 |
| NO855090L (en) | 1986-06-19 |
| PT81690B (en) | 1988-02-17 |
| HU193357B (en) | 1987-09-28 |
| DK166502B1 (en) | 1993-06-01 |
| NO163014B (en) | 1989-12-11 |
| EP0186834A3 (en) | 1986-11-26 |
| FI83089B (en) | 1991-02-15 |
| EP0186834A2 (en) | 1986-07-09 |
| DK587585D0 (en) | 1985-12-17 |
| HUT40138A (en) | 1986-11-28 |
| JPH0662665B2 (en) | 1994-08-17 |
| NZ214449A (en) | 1989-01-06 |
| FI854788A (en) | 1986-06-19 |
| IE58147B1 (en) | 1993-07-14 |
| DE3572670D1 (en) | 1989-10-05 |
| ES8701194A1 (en) | 1986-12-01 |
| CA1262894A (en) | 1989-11-14 |
| ZA859666B (en) | 1986-08-27 |
| NO163014C (en) | 1990-03-21 |
| EP0186834B1 (en) | 1989-08-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO1994022899A1 (en) | New prednisolone derivates | |
| DE2222491C3 (en) | Pregnan series steroid 21-nitric acid esters, medicaments containing them and processes for the preparation thereof | |
| DE1618065C3 (en) | 21-Oxo-23-deoxo-cardenoIides, processes for their production and pharmaceuticals made therefrom | |
| DE2937267C2 (en) | ||
| DE2322655C2 (en) | Prostaglandin F? 2???? Esters, process for their preparation and their use for the purification of prostaglandin F? 2???? | |
| DD202719A5 (en) | PROCESS FOR PREPARING ISOSORBIDE-2-NITRATE | |
| CH621551A5 (en) | ||
| DE3153723C2 (en) | ||
| DD242231A5 (en) | 13-ALKYL-17 BETA (3-ACYLOXY-PROPYL) GONANES | |
| EP0061418B1 (en) | 7-alpha-alkoxycarbonyl-15-beta-16-beta-methylene-4 androstene, process for their preparation and their utilization as pharmaceutical preparations | |
| DE2603596C2 (en) | Glycyrrhetinic acid derivatives, processes for their preparation and pharmaceuticals containing them | |
| DE3308196A1 (en) | METHOD FOR PRODUCING 6'-ALKYL-SPECTINOMYCIN AND ALKYL-SPECTINOMYCIN ANALOGS | |
| DE1620422A1 (en) | Process for the preparation of heterocyclic compounds | |
| DE69206321T2 (en) | Ursane derivatives, their preparation and the pharmaceutical composition containing them. | |
| DE2918954C2 (en) | ||
| EP0063368B1 (en) | Process for the preparation of pregn-4-ene-3,20-dione derivatives and 17-alpha-ethynyl-17-beta-trifluoroacetoxy-gon-4-ene-3-one derivatives, and pharmaceutical compositions containing the latter compounds | |
| DE1568015A1 (en) | New acyl derivatives of proscillaridin A and process for their preparation | |
| CH526527A (en) | 6-alpha methyl-17 alpha-caproyloxy-19-non- - progesterone having progestative and anti- | |
| AT356291B (en) | METHOD FOR THE PRODUCTION OF COMPOUNDS IN THE DIHYDROLYSERIC ACID AND DIHYDROISOLYER SERIES | |
| DE1668661C3 (en) | 6-cyanosteroids and processes for their preparation | |
| CH535235A (en) | 6-nor-6-cyano-lysergic acid derivs - withpharmacological activity | |
| AT253135B (en) | Process for making new steroid compounds | |
| DE1468632C (en) | öalpha Acetylthio 4 en 3 on steroids and process for their production | |
| DE1230795B (en) | Process for the preparation of androstano [2, 3-c] furazan derivatives | |
| DE2109305B2 (en) | 20-Hydroxylated 17 a - MethyI-19-nor-pregna-4,9-dienes, process for their preparation and intermediates |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| ENJ | Ceased due to non-payment of renewal fee |