CH536295A - Oestratriene-3-cyclopentyl ethers oestrogeni - regulators - Google Patents
Oestratriene-3-cyclopentyl ethers oestrogeni - regulatorsInfo
- Publication number
- CH536295A CH536295A CH1870372A CH1870372A CH536295A CH 536295 A CH536295 A CH 536295A CH 1870372 A CH1870372 A CH 1870372A CH 1870372 A CH1870372 A CH 1870372A CH 536295 A CH536295 A CH 536295A
- Authority
- CH
- Switzerland
- Prior art keywords
- oestratriene
- methyl
- delta
- regulators
- cyclopentyl
- Prior art date
Links
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000011541 reaction mixture Substances 0.000 claims description 4
- HLCRYAZDZCJZFG-BDXSIMOUSA-N (8s,9s,13s,14s)-13-methyl-6,7,8,9,11,12,14,15,16,17-decahydrocyclopenta[a]phenanthrene Chemical compound C1CC2=CC=CC=C2[C@@H]2[C@@H]1[C@@H]1CCC[C@@]1(C)CC2 HLCRYAZDZCJZFG-BDXSIMOUSA-N 0.000 claims description 3
- BOTLEXFFFSMRLQ-UHFFFAOYSA-N cyclopentyloxycyclopentane Chemical compound C1CCCC1OC1CCCC1 BOTLEXFFFSMRLQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 2
- 150000004678 hydrides Chemical class 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 230000001076 estrogenic effect Effects 0.000 abstract description 4
- 230000001836 utereotrophic effect Effects 0.000 abstract description 4
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 abstract description 3
- 238000002513 implantation Methods 0.000 abstract description 3
- 230000002401 inhibitory effect Effects 0.000 abstract description 3
- 210000001109 blastomere Anatomy 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 230000035558 fertility Effects 0.000 abstract description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 abstract 1
- 238000003776 cleavage reaction Methods 0.000 abstract 1
- 229910000489 osmium tetroxide Inorganic materials 0.000 abstract 1
- 230000007017 scission Effects 0.000 abstract 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- -1 Lithium aluminum hydride Chemical compound 0.000 description 3
- 241000700159 Rattus Species 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000825 pharmaceutical preparation Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000027326 copulation Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000262 estrogen Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003780 keratinization Effects 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 230000000624 ovulatory effect Effects 0.000 description 1
- 238000007911 parenteral administration Methods 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/56—Compounds containing cyclopenta[a]hydrophenanthrene ring systems; Derivatives thereof, e.g. steroids
- A61K31/565—Compounds containing cyclopenta[a]hydrophenanthrene ring systems; Derivatives thereof, e.g. steroids not substituted in position 17 beta by a carbon atom, e.g. estrane, estradiol
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
- A23K20/168—Steroids
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
- A23K20/184—Hormones
-
- 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
- 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
- C07J75/00—Processes for the preparation of steroids in general
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Animal Husbandry (AREA)
- Zoology (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Endocrinology (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- Pharmacology & Pharmacy (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Medicinal Chemistry (AREA)
- Steroid Compounds (AREA)
Abstract
Substd. oestratriene-3-cyclopentyl ethers, oestrogenic uterotropic, fertility regulators. 7-Alpha-methyl-3-16alpha, 17-trihydroxy-DELTA 1,3,5,(10)-oestratriene-3-cyclopentyl ethers are of formula in which the 17-OH grp. may be alpha or beta, and R is H or acetyl. They may be prepared by etherifying the corres. 3-OH cpd. with cyclopentanol, by reduction of 3-cyclopentyloxy-7alpha-methyl-16alpha-acyloxy-17-keto-DELTA 1,3,5,(10)-oestratriene or by reaction of 3-cyclopentyloxy-7alpha-methyl-DELTA 1,3,5,(10e,16-oestratraene with OsO4 and cleavage of the osmiate. The 16, 17-dihydroxy cpd. may be acetylated if desired. The cpds. have oestrogenic, uterotropic and blastocyte implantation inhibiting activities.
Description
Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung des 3-Cyclopentyläthers von 7,x- -Methyl-3,16,17a-trihydroXydl,3.5'10' -östratrien der Formel
EMI1.1
Diese Verbindung sowie deren 16,17-Diacetat besitzen wertvolle pharmakologische Eigenschaften. So wirken sie vor allem östrogen, uterotrop und/oder Blastocyten-implantationshemmend. Die östrogene Wirksamkeit kann z.B. durch einmalige perorale Applikation im Vaginalkeratinisierungstest bewiesen werden. Dabei wirkt das 1dx,17cs-Diol bereits in Dosen von 0,1-10 mg/kg und das Diacetat in Dosen von 0,1 bis 3 mg/kg.
Die uterotrope Eigenschaft zeigt sich an der weiblichen Ratte nach einmaliger peroraler Applikation dieser Verbindungen bei Dosen von 1-10 mg/kg. Die Blastocyten-implantationshemmende Wirksamkeit des 16 ,17,x-Diols lässt sich an normalen Ratten nach Kopulation mit einer einmal gen Dosis von 0,03 bis 0,3 mg/kg demonstrieren und die Störung der vaginalen und ovulatorischen Zyklen der weiblichen Ratte mit einmaliger peroraler Applikation von 1 mg/kg beheben. Die neuen Verbindungen können somit als östrogene Mittel und zur Steuerung der Fertilität verwendet werden.
Die neue Verbindung der Formel I wird erhalten, wenn man erfindungsgemäss eine Verbindung der Formel
EMI1.2
worin Acyl den Acylrest einer niederaliphatischen Carbonsäure, insbesondere der Essigsäure, darstellt, mit einem Dileichtmetallhydrid reduziert und aus dem Reaktionsgemisch die 16a,17 Dihydroxyverbindung isoliert.
Anschliessend wird, wenn erwünscht das erhaltene 1SK,- 17,K-Diol acetyliert.
Diese Reaktion erfolgt in an sich bekannter Weise.
Als Dlleichtmetallhydrid verwendet man vorzugsweise Lithiumaluminiumhydrid oder Natriumborhydrid, dabei erhält man neben dem gewünschten 16x,17cciProdukt auch die 16α,17ss-Dihydroxyverbindung. Letztere lässt sich aus dem Reaktionsgemisch z.B. durch fraktionierte Kristallisation oder Chromatographie abtrennen.
Eine erhaltene 16z,17K-Dihydroxyverbindung kann, wenn erwünscht, in üblicher Weise ins Diacetat übergeführt werden.
Ausgangsstoffe der Formel II lassen ich in an sich bekannter Weise z.B. durch Verätherung der entsprechenden 3-Hydroxyverbindungen mit Cyclopentanol er halten lassen.
Die erfindungsgemäss erhältliche neue Verbindung der Formel I sowie das Diacetat davon können als Heilmittel in Form von pharmazeutischen Präparaten verwendet werden, welche diese Verbindungen zusammen mit pharmazeutischen, organischen oder anorganischen, festen oder flüssigen Trägerstoffen, die für enterale, insbesondere orale oder parenterale Gabe geeignet sind, enthalten. Für die Bildung derselben kommen solche Stoffe in Frage die mit den neuen Verbindungen nicht reagieren.
Die pharmazeutischen Präparate können in fester oder in flüssiger Form vorliegen. Gegebenenfalls enthalten sie Hilfsstoffe, wie Konserviemngs-, Stabilisierungs-, Netz oder Emulgiermittel, Salze zur Veränderung des osmoti schen Druckes oder Puffer. Sie können auch noch andere therapeutisch wertvolle Stoffe enthalten. Die pharmazeutischen Präparate werden nach an sich üblichen Methoden gewonnen.
Die genannten neuen Verbindungen können auch in der Tiermedizin z.B. in einer der obgenannten Formen, oder in Form von Futtermitteln oder von Zusätzen für Tierfutter verwendet werden. Dabei lassen sich z.B. die üblichen Streck- und Verdünnungsmittel bzw. Futtermittel anwenden.
In den folgenden Beispielen sind die Temperaturen in Celsiusgraden angegeben.
Beispiel I
Zu einer Suspension von 2,85 g Lithiumaluminium hydrid in 285 ml Tetrahydrofuran gibt man bei ca. 10
150C eine Lösung von 7,7 g 3cyclopentyloxy-17-acet- oxy-7α-methyl-16α,17α-epoxy-#1,3,5(10) -östratrien in 285 ml Tetrahydrofuran und kocht nach dem Nachspülen mit
140 ml Tetrahydrofuran 2 Stunden am Rückflusskühler.
Man gibt bei ca. 100C vorsichtig 30 ml Essigester, an schliessend 550 ml 2 n Salzsäure und dann 1 Liter Chloroform zu, rührt 10 Minuten bei Zimmertemperatur und trennt die organische Schicht ab. Der Extrakt wird mit Wasser gewaschen, über Natriumsulfat getrocknet und im Wasserstrahlvakuum zur Trockne eingedampft. Nach Adsorption des anfallenden Schaumes an 50facher Menge Silicagel und Eluieren mit einem Gemisch aus Toluol und Essigester (95: 5) erhält man das amorphe 3-Cyclopentyl OXy - 7a - methyl - 1Za,17a-dihydroxy ,\19335 (10) ¯ östratrien.
[iD = + 32 .
Das als Ausgangsmaterial dienende 3-Cyclopentyloxy- -7α-methyl-16α,17α-epoxy-#1,3,5(10)-östratrien wird durch Verätherung von 7α-Methyl-öston mit Cyclopentanol, Überführen des erhaltenen 3-Cyclopentyläthers ins 17 -Enolacetat, z.B. durch Erwärmen mit Acetanhydrid in Pyridin und Umsetzen des erhaltenen 17-Enolacetats mit m-Chlorperbenzoesäure erhalten.
Beispiel 2
5,5 g 3 Cyclopentyloxy-7-methyl- 16cc,17,cc-dihydroxy- -Al 35(l0)-östratrien werden in 35 ml Pyridin gelöst, mit 35 ml Acetanhydrid versetzt und 18 Stunden bei Raumtemperatur stehen gelassen. Das Reaktionsgemisch wird auf Eis/Wasser ausgetragen, eine Stunde gerührt und mit Äther wie üblich aufgearbeitet. Das erhaltene Rohprodukt wird an Silicagel chromatographiert und liefert das reine amorphe 3-Cyclopentyloxy-7α-methyl-16α,17α-diacetoxy- dls35fl0)-östratrien. UV.Spektrum: 223 nm (± = 9000),
279 nm (s = 2000) und 288 nm ( = 1870). [slD = + 140 (CHC13).
The present invention relates to a process for the preparation of the 3-cyclopentyl ether of 7, x-methyl-3,16,17a-trihydroXydl, 3.5'10 '-estratriene of the formula
EMI1.1
This compound and its 16,17-diacetate have valuable pharmacological properties. They have an estrogenic, uterotropic and / or blastocyte implantation-inhibiting effect. The estrogenic activity can e.g. can be proven by a single oral application in the vaginal keratinization test. The 1dx, 17cs diol is effective in doses of 0.1-10 mg / kg and the diacetate in doses of 0.1 to 3 mg / kg.
The uterotropic property is evident in the female rat after a single oral application of these compounds at doses of 1-10 mg / kg. The blastocyte-implantation-inhibiting effectiveness of the 16, 17, x-diol can be demonstrated in normal rats after copulation with a single dose of 0.03 to 0.3 mg / kg and the disturbance of the vaginal and ovulatory cycles of the female rat with a single dose correct peroral application of 1 mg / kg. The new compounds can thus be used as estrogenic agents and for controlling fertility.
The new compound of the formula I is obtained when, according to the invention, a compound of the formula
EMI1.2
wherein acyl is the acyl radical of a lower aliphatic carboxylic acid, in particular acetic acid, reduced with a dichlorometal hydride and the 16a, 17 dihydroxy compound isolated from the reaction mixture.
If desired, the 1SK, -17, K-diol obtained is then acetylated.
This reaction takes place in a manner known per se.
Lithium aluminum hydride or sodium borohydride are preferably used as the light metal hydride, and the 16α, 17ss-dihydroxy compound is obtained in addition to the desired 16x, 17cci product. The latter can be extracted from the reaction mixture e.g. separate by fractional crystallization or chromatography.
A 16z, 17K-dihydroxy compound obtained can, if desired, be converted into the diacetate in the usual way.
I let starting materials of the formula II in a manner known per se, e.g. by etherification of the corresponding 3-hydroxy compounds with cyclopentanol he can keep.
The novel compound of formula I obtainable according to the invention and the diacetate thereof can be used as medicaments in the form of pharmaceutical preparations which combine these compounds with pharmaceutical, organic or inorganic, solid or liquid carriers which are suitable for enteral, in particular oral or parenteral administration , contain. Substances that do not react with the new compounds are suitable for the formation of the same.
The pharmaceutical preparations can be in solid or liquid form. They may contain auxiliaries such as preservatives, stabilizers, wetting agents or emulsifiers, salts for changing the osmotic pressure or buffers. They can also contain other therapeutically valuable substances. The pharmaceutical preparations are obtained according to conventional methods.
The new compounds mentioned can also be used in veterinary medicine, e.g. in one of the forms mentioned above, or in the form of feed or additives for animal feed. For example, use the usual extenders and thinners or feed.
In the following examples the temperatures are given in degrees Celsius.
Example I.
To a suspension of 2.85 g of lithium aluminum hydride in 285 ml of tetrahydrofuran is added at about 10
150C a solution of 7.7 g of 3cyclopentyloxy-17-acet-oxy-7α-methyl-16α, 17α-epoxy- # 1,3,5 (10) -estratriene in 285 ml of tetrahydrofuran and boils with it after rinsing
140 ml of tetrahydrofuran for 2 hours on the reflux condenser.
At about 100 ° C., 30 ml of ethyl acetate, then 550 ml of 2N hydrochloric acid and then 1 liter of chloroform are carefully added, the mixture is stirred for 10 minutes at room temperature and the organic layer is separated off. The extract is washed with water, dried over sodium sulfate and evaporated to dryness in a water-jet vacuum. After adsorption of the foam produced on 50 times the amount of silica gel and elution with a mixture of toluene and ethyl acetate (95: 5), the amorphous 3-cyclopentyl OXy-7a-methyl-1Za, 17a-dihydroxy, \ 19335 (10) ¯ estatriene is obtained.
[iD = + 32.
The 3-cyclopentyloxy-7α-methyl-16α, 17α-epoxy- # 1,3,5 (10) -estratriene serving as starting material is prepared by etherification of 7α-methyl-ozone with cyclopentanol, converting the obtained 3 -Cyclopentyl ether into 17 -enol acetate, e.g. obtained by heating with acetic anhydride in pyridine and reacting the 17-enol acetate obtained with m-chloroperbenzoic acid.
Example 2
5.5 g of 3 cyclopentyloxy-7-methyl-16cc, 17, cc-dihydroxy-Al 35 (10) -estratriene are dissolved in 35 ml of pyridine, mixed with 35 ml of acetic anhydride and left to stand for 18 hours at room temperature. The reaction mixture is poured onto ice / water, stirred for one hour and worked up with ether as usual. The crude product obtained is chromatographed on silica gel and gives the pure amorphous 3-cyclopentyloxy-7α-methyl-16α, 17α-diacetoxy-dls35fl0) -estratriene. UV spectrum: 223 nm (± = 9000),
279 nm (s = 2000) and 288 nm (= 1870). [slD = +140 (CHC13).
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1870372A CH536295A (en) | 1970-04-24 | 1970-04-24 | Oestratriene-3-cyclopentyl ethers oestrogeni - regulators |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1870372A CH536295A (en) | 1970-04-24 | 1970-04-24 | Oestratriene-3-cyclopentyl ethers oestrogeni - regulators |
| CH621970A CH551959A (en) | 1970-04-24 | 1970-04-24 | Oestratriene-3-cyclopentyl ethers oestrogeni - regulators |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH536295A true CH536295A (en) | 1973-04-30 |
Family
ID=4306158
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH1870372A CH536295A (en) | 1970-04-24 | 1970-04-24 | Oestratriene-3-cyclopentyl ethers oestrogeni - regulators |
| CH621970A CH551959A (en) | 1970-04-24 | 1970-04-24 | Oestratriene-3-cyclopentyl ethers oestrogeni - regulators |
| CH1870272A CH536290A (en) | 1970-04-24 | 1970-04-24 | Oestratriene-3-cyclopentyl ethers oestrogeni - regulators |
Family Applications After (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH621970A CH551959A (en) | 1970-04-24 | 1970-04-24 | Oestratriene-3-cyclopentyl ethers oestrogeni - regulators |
| CH1870272A CH536290A (en) | 1970-04-24 | 1970-04-24 | Oestratriene-3-cyclopentyl ethers oestrogeni - regulators |
Country Status (5)
| Country | Link |
|---|---|
| AT (1) | AT312826B (en) |
| CH (3) | CH536295A (en) |
| CS (1) | CS157120B2 (en) |
| SU (1) | SU434651A3 (en) |
| ZA (1) | ZA712525B (en) |
-
1970
- 1970-04-24 CH CH1870372A patent/CH536295A/en not_active IP Right Cessation
- 1970-04-24 CH CH621970A patent/CH551959A/en not_active IP Right Cessation
- 1970-04-24 CH CH1870272A patent/CH536290A/en not_active IP Right Cessation
-
1971
- 1971-04-20 ZA ZA712525A patent/ZA712525B/en unknown
- 1971-04-23 CS CS173973*1A patent/CS157120B2/cs unknown
- 1971-04-23 SU SU1815023A patent/SU434651A3/en active
- 1971-04-23 AT AT273172A patent/AT312826B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| ZA712525B (en) | 1972-01-26 |
| CH536290A (en) | 1973-04-30 |
| CH551959A (en) | 1974-07-31 |
| AT312826B (en) | 1974-01-25 |
| SU434651A3 (en) | 1974-06-30 |
| CS157120B2 (en) | 1974-08-23 |
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