CH223206A - Process for the preparation of a polyhydric alcohol of the cyclopentanopolyhydrophenanthrene series. - Google Patents
Process for the preparation of a polyhydric alcohol of the cyclopentanopolyhydrophenanthrene series.Info
- Publication number
- CH223206A CH223206A CH223206DA CH223206A CH 223206 A CH223206 A CH 223206A CH 223206D A CH223206D A CH 223206DA CH 223206 A CH223206 A CH 223206A
- Authority
- CH
- Switzerland
- Prior art keywords
- oxygen
- releasing agent
- preparation
- polyhydric alcohol
- acid
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 10
- 150000005846 sugar alcohols Polymers 0.000 title description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- IVBTWIITBMTVLS-WWDXVDCESA-N (8R,9S,10S,13R,14S,17R)-17-ethyl-10,13-dimethyl-2,3,4,5,6,7,8,9,11,12,14,17-dodecahydro-1H-cyclopenta[a]phenanthrene-15,15,16,16-tetrol Chemical compound OC1(C([C@@H]2[C@]([C@H]1CC)(C)CC[C@H]1[C@H]2CCC2CCCC[C@]12C)(O)O)O IVBTWIITBMTVLS-WWDXVDCESA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000012736 aqueous medium Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 239000012285 osmium tetroxide Substances 0.000 claims description 2
- 229910000489 osmium tetroxide Inorganic materials 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims 2
- 239000013078 crystal Substances 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 claims 1
- 238000006460 hydrolysis reaction Methods 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- MDKXBBPLEGPIRI-UHFFFAOYSA-N ethoxyethane;methanol Chemical compound OC.CCOCC MDKXBBPLEGPIRI-UHFFFAOYSA-N 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- -1 osmium ester Chemical class 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J7/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of two carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J5/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, substituted in position 17 beta by a chain of two carbon atoms, e.g. pregnane and substituted in position 21 by only one singly bound oxygen atom, i.e. only one oxygen bound to position 21 by a single bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J75/00—Processes for the preparation of steroids in general
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung eines mehrwertigen Alkohols der Cyelopentanopolyhydro- phenanthrenreihe. Gegenstand des vorliegenden Patentes ist ein Verfahren zur Herstellung von Pregnan- tetrol-(3.17.20.21), das dadurchgekennzeich- net ist, dass man auf 3. 17-Dioxy-17 -äthenyl- androstan ein Sauerstoff abgebendes Mittel und auf die hierbei entstehende Verbin dung ein hydrolysierendes Mittel einwirken lä.sst.
Als Sauerstoff abgebende Mittel verwen det man vorteilhaft Benzopersäure, Phthal- persäure, Osmiumtetroxy d, Wasserstoffsuper oxyd, Peressigsäure usw. Die entstandenen Zwischenprodukte verseift man zum Beispiel durch Erhitzen im wässrigen Medium im Bombenrohr.
Die neue Verbindung soll als Arznei mittel oder als Zwischenprodukt bei der Her stellung von Arzneimitteln Verwendung finden.
Beispiel <I>1:</I> 1,6 g 3.17-Dioxy-17-äthenylandrostan werden in ätherischer Lösung mit 1,3 g Osmiumtetroxyd versetzt. Nach einigen Stunden fällt ein feiner, schwarzer Nieder schlag aus, der nach 2 Tagen abfiltriert wird. Dieser abfiltrierte Osmiumester wird in alkoholischer Lösung mit Natriumsulfit 1 Stunde am Rückfluss erhitzt. Man filtriert ab und kocht den Niederschlag mit Alkohol aus.
Die alkoholischen Filtrate werden in Äther aufgenommen und mit Alkali und Wasser mehrfach gewaschen. Aus der ätheri schen Lösung fällt das Pregnantetrol- (3. 17. 20. 21) aus (Schmelzpunkt 227 ). Es kann durch Umkristallisieren aus Äther oder verdünntem Aceton noch weiter gerei nigt werden und schmilzt dann bei 229 bis 231 . Ams den Mutterlaugen lässt sich 3. 17- Dioxy-17-aldehydoandrostan isolieren, das durch Sprengung der Athenyl-Doppelbindung entstanden ist.
Beispiel <I>2:</I> 3,69 g 3.17-Dioxy-17-äthenylandrostan werden in Chloroform gelöst und nach Zu- satz von 7 g Phthalmonopersäure in 90 cm' Chloroform im Dunkeln bei Zimmertempera tur über Nacht stehen gelassen. Nach dieser Zeit ist die theoretische Menge von 2,1 g Persäure verbraucht. Es wird nunmehr in Äther aufgenommen und der Äther mit ver dünntem Alkali gewaschen.
Nach Verdamp fen des Äthers wird der Rückstand aus ver dünntem Methanol umkristallisiert. Die Aus beute beträgt 2,6 g des entsprechenden Oxyds vom Schmelzpunkt 182 . 0,2 g 3. 17-Dioxy- 17-äthylenoxydoandrostan wurden mit 4 cm' Wasser 20 Stunden im Bombenrohr auf 190 bis 200' erhitzt. Das Reaktionsprodukt wird in Äther aufgenommen, der Äther getrocknet und zum grössten Teil verdampft. Während des Eindampfens scheidet sich das entste hende Pregnantetrol-(3. 17 .20.21) ab, das abfiltriert wird. Es lässt sich durch Um kristallisieren aus Äther oder aus Methanol äther reinigen.
Process for the production of a polyhydric alcohol of the Cyelopentanopolyhydro- phenanthren range. The subject matter of the present patent is a process for the production of pregnantetrol (3.17.20.21), which is characterized in that an oxygen-releasing agent is applied to 3. 17-dioxy-17-ethenylandrostane and the resulting compound dung allows a hydrolyzing agent to act.
The oxygen-releasing agent used is advantageously benzoperic acid, phthalic acid, osmium tetroxy d, hydrogen superoxide, peracetic acid, etc. The intermediate products formed are saponified, for example, by heating in an aqueous medium in a sealed tube.
The new compound is intended to be used as a drug or as an intermediate in the manufacture of drugs.
Example <I> 1 </I> 1.6 g of 3.17-dioxy-17-ethenylandrostane are mixed with 1.3 g of osmium tetroxide in an ethereal solution. After a few hours, a fine, black precipitate falls out, which is filtered off after 2 days. This filtered off osmium ester is refluxed for 1 hour in alcoholic solution with sodium sulfite. It is filtered off and the precipitate is boiled off with alcohol.
The alcoholic filtrates are taken up in ether and washed several times with alkali and water. Pregnantetrol- (3. 17. 20. 21) precipitates from the ethereal solution (melting point 227). It can be further purified by recrystallization from ether or dilute acetone and then melts at 229 to 231. From the mother liquors it is possible to isolate 3. 17-dioxy-17-aldehydoandrostane, which was formed by breaking the athenyl double bond.
Example <I> 2: </I> 3.69 g of 3.17-dioxy-17-ethenylandrostane are dissolved in chloroform and, after the addition of 7 g of phthalmonoperic acid in 90 cm 'chloroform, left to stand overnight in the dark at room temperature. After this time, the theoretical amount of 2.1 g of peracid has been consumed. It is now taken up in ether and the ether washed with ver diluted alkali.
After evaporation of the ether, the residue is recrystallized from dilute methanol ver. The yield is 2.6 g of the corresponding oxide with a melting point of 182. 0.2 g of 3. 17-Dioxy-17-Ethylenoxydoandrostan were heated with 4 cm 'of water in a sealed tube to 190 to 200' for 20 hours. The reaction product is taken up in ether, the ether is dried and for the most part evaporated. During the evaporation, the resulting Pregnantetrol (3. 17 .20.21) separates out, which is filtered off. It can be purified by recrystallizing it from ether or from methanol ether.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE223206X | 1936-07-14 | ||
| CH214399T | 1939-05-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH223206A true CH223206A (en) | 1942-08-31 |
Family
ID=25725579
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH223206D CH223206A (en) | 1936-07-14 | 1937-07-09 | Process for the preparation of a polyhydric alcohol of the cyclopentanopolyhydrophenanthrene series. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH223206A (en) |
-
1937
- 1937-07-09 CH CH223206D patent/CH223206A/en unknown
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