CH536290A - Oestratriene-3-cyclopentyl ethers oestrogeni - regulators - Google Patents
Oestratriene-3-cyclopentyl ethers oestrogeni - regulatorsInfo
- Publication number
- CH536290A CH536290A CH1870272A CH1870272A CH536290A CH 536290 A CH536290 A CH 536290A CH 1870272 A CH1870272 A CH 1870272A CH 1870272 A CH1870272 A CH 1870272A CH 536290 A CH536290 A CH 536290A
- Authority
- CH
- Switzerland
- Prior art keywords
- methyl
- formula
- compound
- cyclopentyloxy
- estratriene
- Prior art date
Links
- 230000001076 estrogenic effect Effects 0.000 claims abstract description 6
- 229910000489 osmium tetroxide Inorganic materials 0.000 claims abstract description 6
- 230000001836 utereotrophic effect Effects 0.000 claims abstract description 6
- 238000002513 implantation Methods 0.000 claims abstract description 5
- 230000002401 inhibitory effect Effects 0.000 claims abstract description 5
- 210000001109 blastomere Anatomy 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 3
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000035558 fertility Effects 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 6
- 241000700159 Rattus Species 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 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 5
- 238000000034 method Methods 0.000 claims description 5
- 239000012285 osmium tetroxide Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 4
- 239000012043 crude product Substances 0.000 claims description 4
- BOTLEXFFFSMRLQ-UHFFFAOYSA-N cyclopentyloxycyclopentane Chemical compound C1CCCC1OC1CCCC1 BOTLEXFFFSMRLQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003814 drug Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- -1 lithium aluminum hydride Chemical compound 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052762 osmium Inorganic materials 0.000 claims description 4
- 239000000825 pharmaceutical preparation Substances 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 4
- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 239000007858 starting material Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000002211 ultraviolet spectrum Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 2
- 239000004606 Fillers/Extenders Substances 0.000 claims description 2
- 229930195725 Mannitol Natural products 0.000 claims description 2
- 241001465754 Metazoa Species 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- BRTFVKHPEHKBQF-UHFFFAOYSA-N bromocyclopentane Chemical compound BrC1CCCC1 BRTFVKHPEHKBQF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000872 buffer Substances 0.000 claims description 2
- 239000000969 carrier Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 230000027326 copulation Effects 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims description 2
- 239000003995 emulsifying agent Substances 0.000 claims description 2
- 239000000262 estrogen Substances 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 238000006266 etherification reaction Methods 0.000 claims description 2
- 230000007717 exclusion Effects 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 230000003780 keratinization Effects 0.000 claims description 2
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 2
- 239000000594 mannitol Substances 0.000 claims description 2
- 235000010355 mannitol Nutrition 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 230000003204 osmotic effect Effects 0.000 claims description 2
- 230000000624 ovulatory effect Effects 0.000 claims description 2
- 238000007911 parenteral administration Methods 0.000 claims description 2
- 230000000144 pharmacologic effect Effects 0.000 claims description 2
- 239000003755 preservative agent Substances 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 238000006894 reductive elimination reaction Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 239000002966 varnish Substances 0.000 claims description 2
- 239000000080 wetting agent Substances 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 abstract 1
- 238000003776 cleavage reaction Methods 0.000 abstract 1
- 230000007017 scission Effects 0.000 abstract 1
- 238000004519 manufacturing process Methods 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 70c- iMethyl-3,1ic,17-trihydroxytl 3 5fl0)-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 16o,17,x 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 llSx,17lx-Diols lässt sich an normalen Ratten nach Kopulation mit einer einmaligen Dosis von 0,03 bis 0,3 mg/kg demonstrieren und die Störung der vaginalen und ovulatorischen Zyklen des 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
mit Osmiumtetroxyd behandelt und das erhaltene Osmiat reduktiv spaltet. Anschliessend wird, wenn erwünscht, das erhaltene 1Scc,170c-Diol acetyliert.
Diese Reaktion erfolgt in an sich bekannter Weise.
Die reduktive Spaltung des Osmiats lässt sich z.B. mit einer wässrigen Lösung von Mannit, Natriumbisulfit oder mit Lithiumaluminiumhydrid bewerkstelligen.
Ausgangsstoffe der Formel II lassen sich in an sich bekannter Weise z.B. durch Verätherung der entsprechenden 3-Hydroxyverbindungen mit Cyclopentanol erhalten.
Die erfindungsgemäss erhältliche 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 Form oder in flüssiger Form vorliegen. Gegebenenfalls enthalten sie Hilfsstoffe, wie Konservierungs-, Stabilisierungs-, Netzoder Emulgiermittel, Salze zur Veränderung des osmotischen Druckes oder Puffer. Sie können auch noch andere therapeutisch wertvolle Stoffe enthalten.
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 ich z.B. die üblichen Streck- und Verdünnungsmittel bzw. Futtermittel anwenden.
In den folgenden Beispielen sind die Temperaturen in Celsiusgraden angegeben.
Beispiel 1
4,5 g 3-Cyclopentyloxy-7α-methyl-#1,3,5(10),16-östrate- traen werden in 450 ml absolutem Äther und 4,5 ml Pyridin gelöst und bei Zimmertemperatur mit 4,1 g Osmium tetroxid in 60 ml absolutem Äther versetzt und 3 Tage bei Raumtemperatur unter Lichtausschluss stehen gelas sen. Man nutscht den Osmiumester ab, wäscht mit Äther nach und kocht ihn mit 420 ml 95%igem Äthylalkohol und 420 ml 5taiger Natriumhydrogensulfitlösung 2 Stun den unter Rückfluss. Man trennt nach dem Abkühlen auf Zimmertemperatur das ausgefallene Osmium über Celite ab, engt das Filtrat im Wasserstrahlvakuum ein, versetzt es mit Wasser und extrahiert zweimal mit Chloroform.
Die organischen Lösungen werden mit Wasser gewaschen, getrocknet und im Wasserstrahlvakuum eingedampft. Das erhaltene Rohprodukt wird in Toluol gelöst und an 50 facher Gewichtsmenge Silicagel chromatographiert. Man erhält so das reine amorphe 3-Cyclopentyloxy-7α-methyl- -16α,17α-dihydroxy-#1,3,5(10)-östratrien. [α]D = + 32 .
Die Verbindung liegt in der Form eines farblosen Lacks vor. UV.-Spektrum: 280 nm (e = 2000), 288 nm (e =
1900).
Das als Ausgangsmaterial dienende 3 ydopentyloxy- -7,x-methyl-A135fl0) stratetraen wird durch Umsetzen der entsprechenden freien 3-Hydroxy-Verbindung mit
Cyclopentylbromid erhalten.
Beispiel 2
5,5 g des gemäss Beispiel 1 erhaltenen 3-Cyclopentyl- oxy - 7α - methyl - 16α,17α-dihydroxy - #1,3,5(10)-östratriens werden in 35 ml Pyridin gelöst, mit 35 ml Acetanhydrid versetzt und 18 Stunden bei Raumtemperatur stehen ge lassen. Das Reaktionsgemisch wird auf Eis/Wasser aus getragen, eine Stunde gerührt und mit Äther wie üblich aufgearbeitet. Das erhaltene Rohprodukt wird an Silica gel chromatographiert und liefert das reine amorphe 3 -Cyclopentyloxy -7x - methyl-16x,17x - diacetoxy-A1,3,5 (10) - -östratrien. UV.-Spektrum: 223 nm (e = 9000), 279 nm (± = 2000) und 288 nm (e =1870). ilD = + 140 (CHCI3).
PATENTANSPRUCH
Verfahren zur Herstellung des östrogen hochwirksa men 3 -Cyclopentyläthers von 7α-Methyl-3,16α,17α-tri-
**WARNUNG** Ende DESC Feld konnte Anfang CLMS uberlappen**.
The present invention relates to a process for the preparation of the 3 cyclopentyl ether of 70c-iMethyl-3,1ic, 17-trihydroxytl 3 5fl0) -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 16o, 17, x diol already works 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 llSx, 17lx-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 oral application of 1 mg / kg fix. 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
treated with osmium tetroxide and reductively cleaves the osmate obtained. If desired, the 1Scc, 170c-diol obtained is then acetylated.
This reaction takes place in a manner known per se.
The reductive cleavage of the osmate can be e.g. accomplish with an aqueous solution of mannitol, sodium bisulfite or with lithium aluminum hydride.
Starting materials of the formula II can be used in a manner known per se, e.g. obtained by etherification of the corresponding 3-hydroxy compounds with cyclopentanol.
The compound of the 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, especially oral or parenteral administration, contain. Substances that do not react with the new compounds come into question for the formation of the same. The pharmaceutical preparations can be in solid form or in 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 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. I leave e.g. use the usual extenders and thinners or feed.
In the following examples the temperatures are given in degrees Celsius.
example 1
4.5 g of 3-cyclopentyloxy-7α-methyl- # 1,3,5 (10), 16-estratetra are dissolved in 450 ml of absolute ether and 4.5 ml of pyridine and at room temperature with 4.1 g of osmium tetroxide in 60 ml of absolute ether and left to stand for 3 days at room temperature under exclusion of light. The osmium ester is filtered off with suction, rewashed with ether and refluxed for 2 hours with 420 ml of 95% ethyl alcohol and 420 ml of 5-day sodium hydrogen sulfite solution. After cooling to room temperature, the precipitated osmium is separated off on Celite, the filtrate is concentrated in a water-jet vacuum, water is added and the mixture is extracted twice with chloroform.
The organic solutions are washed with water, dried and evaporated in a water jet vacuum. The crude product obtained is dissolved in toluene and chromatographed on 50 times the amount by weight of silica gel. The pure amorphous 3-cyclopentyloxy-7α-methyl-16α, 17α-dihydroxy- # 1,3,5 (10) -estratriene is thus obtained. [α] D = + 32.
The connection is in the form of a colorless varnish. UV spectrum: 280 nm (e = 2000), 288 nm (e =
1900).
The 3-ydopentyloxy- 7, x-methyl-A135fl0) stratetraene used as the starting material is converted into the corresponding free 3-hydroxy compound with
Cyclopentyl bromide obtained.
Example 2
5.5 g of the 3-cyclopentyloxy-7? - methyl - 16α, 17α-dihydroxy - # 1,3,5 (10) -estratriene are dissolved in 35 ml of pyridine, 35 ml of acetic anhydride are added and the mixture is left to stand for 18 hours at room temperature. The reaction mixture is carried out on 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-7x-methyl-16x, 17x-diacetoxy-A1,3,5 (10) - -estratriene. UV spectrum: 223 nm (e = 9000), 279 nm (± = 2000) and 288 nm (e = 1870). ilD = +140 (CHCI3).
PATENT CLAIM
Process for the production of the highly estrogenically active 3-cyclopentyl ether of 7α-methyl-3,16α, 17α-tri
** WARNING ** End of DESC field could overlap beginning of CLMS **.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1870272A CH536290A (en) | 1970-04-24 | 1970-04-24 | Oestratriene-3-cyclopentyl ethers oestrogeni - regulators |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1870272A CH536290A (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 |
|---|---|
| CH536290A true CH536290A (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 Before (2)
| 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 |
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 |
| CH551959A (en) | 1974-07-31 |
| AT312826B (en) | 1974-01-25 |
| CH536295A (en) | 1973-04-30 |
| SU434651A3 (en) | 1974-06-30 |
| CS157120B2 (en) | 1974-08-23 |
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