CH238258A - Process for the preparation of a ketone of the cyclopentanopolyhydrophenanthrene series. - Google Patents
Process for the preparation of a ketone of the cyclopentanopolyhydrophenanthrene series.Info
- Publication number
- CH238258A CH238258A CH238258DA CH238258A CH 238258 A CH238258 A CH 238258A CH 238258D A CH238258D A CH 238258DA CH 238258 A CH238258 A CH 238258A
- Authority
- CH
- Switzerland
- Prior art keywords
- preparation
- ketone
- cyclopentanopolyhydrophenanthrene series
- formula
- water
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 4
- 150000002576 ketones Chemical class 0.000 title description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- RJKFOVLPORLFTN-LEKSSAKUSA-N Progesterone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H](C(=O)C)[C@@]1(C)CC2 RJKFOVLPORLFTN-LEKSSAKUSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229960003387 progesterone Drugs 0.000 claims description 2
- 239000000186 progesterone Substances 0.000 claims description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M bisulphate group Chemical group S([O-])(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- -1 enol compound Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- MNRHZPCIEGLWGK-LEKSSAKUSA-N pregn-5-ene-3,20-dione Chemical compound C1C=C2CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H](C(=O)C)[C@@]1(C)CC2 MNRHZPCIEGLWGK-LEKSSAKUSA-N 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 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)
- Steroid Compounds (AREA)
Description
Terfahren zur Darstellung eines Betons der Cyclopentanopolyhydrophenanthren-Reihe. Es wurde gefunden, dass man zu Progesteron gelangen kann, wenn man die Verbindung der Formel
EMI0001.0003
mit wasserabspaltenden Mitteln behandelt. Die Abspaltung von Wasser kann z. B.
mit den für diese Reaktion bekannterweise geeigneten Mitteln erfolgen, z. B. unter der Einwirkung von Mineralsäuren, vorzugsweise in alkoholischer Lösung, in Dioxan oder der gleichen, von Phosphoroxychlorid, Bisul- faten, von Ameisensäure, Oxalsäure, von Säureanhydriden, wie Acetanhydrid oder Phosphorpentoxyd, durch die Wirkung von Katalysatoren, wie Jod.
An Stelle der oder in Kombination mit den angegebenen Mitteln kann man auch andere entsprechende Mass nahmen anwenden, wie z. B. erhöhte Tempe ratur, wobei man gegebenenfalls in Gegen wart indifferenter Gase oder unter vermin dertem Druck arbeitet.
Das vorliegende Verfahren verläuft nach dem folgenden Reaktionsschema:
EMI0001.0019
Wie Versuche ergeben haben, entsteht aus dem freien sekundären Alkohol (Formel I) hauptsächlich die freie Enolverbindung (For mel II), die. als solche unbeständig, sich in das entsprechende Keton (In) umlagert bezw. mit ihm tautomer ist.
Das nach dem neuen Verfahren erhaltene bekannte A4,5_pregnen-3,20-dion kann thera- peutische Verwendung finden oder als Zwi schenprodukt zur Herstellung therapeutisch wertvoller Verbindungen dienen.
<I>Beispiel:</I> 1 Teil 5,17,20-Trioxy-prebnanon-(3) wird mit 60 Teilen Propylalkohol und 5 Teilen 30%iger Schwefelsäure 20 Minuten am Rückfluss gekocht. Dann giesst man in Wasser, äthert aus, wäscht die ätherische Lösung mit Wasser, trocknet sie und dampft sie im Vakuum ein. Aus dem Rückstand ge winnt man z.
B. über das schwerlösliche Disemicarbazon, durch Sublimation, fraktio nierte Kristallisation und/oder auswählende Adsorption in üblicher Weise das Probesteroit der Formel
EMI0002.0015
das aus verdünntem Alkohol in dimorphen i#lodifikationen kristallisiert. die bei 120 bezw. 129 schmelzen.
Terfahren to represent a concrete of the cyclopentanopolyhydrophenanthrene series. It has been found that progesterone can be obtained by using the compound of the formula
EMI0001.0003
treated with water-releasing agents. The elimination of water can, for. B.
take place with the means known to be suitable for this reaction, e.g. B. under the action of mineral acids, preferably in alcoholic solution, in dioxane or the like, of phosphorus oxychloride, bisulfates, of formic acid, oxalic acid, of acid anhydrides such as acetic anhydride or phosphorus pentoxide, through the action of catalysts such as iodine.
Instead of or in combination with the specified means, you can also apply other appropriate measures, such. B. increased Tempe temperature, where you may work in the presence of inert gases or under reduced pressure.
The present process proceeds according to the following reaction scheme:
EMI0001.0019
As experiments have shown, the free secondary alcohol (formula I) mainly results in the free enol compound (formula II), which. as such inconsistent, rearranged or respectively in the corresponding ketone (In). is tautomeric with him.
The known A4,5_pregnen-3,20-dione obtained by the new process can be used therapeutically or as an intermediate product for the production of therapeutically valuable compounds.
<I> Example: </I> 1 part 5,17,20-trioxy-prebnanon- (3) is refluxed for 20 minutes with 60 parts propyl alcohol and 5 parts 30% sulfuric acid. Then you pour into water, ether out, wash the ethereal solution with water, dry it and evaporate it in a vacuum. From the residue you win z.
B. over the sparingly soluble disemicarbazone, by sublimation, fractional crystallization and / or selective adsorption in the usual way the Probesteroit of the formula
EMI0002.0015
which crystallizes from dilute alcohol in dimorphic i # iodifications. those at 120 respectively. 129 melt.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH207495T | 1937-06-05 | ||
| CH238258T | 1938-04-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH238258A true CH238258A (en) | 1945-06-30 |
Family
ID=25724404
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH238258D CH238258A (en) | 1937-06-05 | 1938-04-22 | Process for the preparation of a ketone of the cyclopentanopolyhydrophenanthrene series. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH238258A (en) |
-
1938
- 1938-04-22 CH CH238258D patent/CH238258A/en unknown
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