CH245274A - Process for the preparation of a new compound of the cyclopentanopolyhydrophenanthrene series. - Google Patents
Process for the preparation of a new compound of the cyclopentanopolyhydrophenanthrene series.Info
- Publication number
- CH245274A CH245274A CH245274DA CH245274A CH 245274 A CH245274 A CH 245274A CH 245274D A CH245274D A CH 245274DA CH 245274 A CH245274 A CH 245274A
- Authority
- CH
- Switzerland
- Prior art keywords
- acetoxy
- dione
- preparation
- new compound
- split
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J9/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J3/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, substituted in position 17 beta by one carbon atom
-
- 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
- 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
- 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)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Steroid Compounds (AREA)
Description
Verfahren zur Herstellung einer neuen Verbindung der Cyclopentanopolyhydr ophenanthr en-RReihe. Es wurde gefunden, dass man zu einer im Ring C ungesättigten Verbindung der Cyclo- pentanopolyhydrophenanthren-Reihe gelan gen kann, wenn. man ein 21-Acetoxy-pregnan- d,20-dion,
das im Ring C in 12-Stellung einen zusammen mit einem benachbarten Wasser stoffatom abspaltbaren _Substituenten auf weist, mit diesen Substituenten unter Bil- dung einer Doppelbindung abspaltenden Mit teln behandelt.
Der 12ständige, zusammen mit einem be nachbarten Wasserstoffatom abspaltbare Sub- stituent des Ausgangsstoffes kann eine freie Hydroxylgruppe oder eine beispielsweise durch Carbonsäuren, wie Essig-, Propion- oder Benzoesäure, durch Sulfonsäure,
Ha logenwasserstoffsäuren oder Xanthogensäuren veresterte Hydroxylgruppe sein.
Die Abspaltung dieses Substituenten unter Bildung einer Doppelbindung kann mit den für diese Reaktion an sich bekannten Mitteln erfolgen. Beispielsweise lässt sich eine freie Hydroxylgruppe unter der Einwirkung von Mineralsäuren, vorzugsweise in Lösungs- mitteln, wie Eisessig, Alkohol, Dioxan und dergleichen., von Phosphoroxychlorid, 'Bisul- faten, von Ameisensäure,
Oxalsäure, von Säureanhydriden, wie Acetanhydrid oder Phosphorpentoxyd, oder durch die Einwir kung von Katalysatoren, wie Jod- oder Car- bonsäure-Salzen, abspalten.
Eine veresterte Hydroxylgruppe wird ausser durch die ge nannten Mittel vorzugsweise auch mit Al- kalien. Erdalkalien, Carbonaten, organischen Basen, wie Pyridin, Dimethylanilin usw., ab gespalten.
An Stelle oder in Kombination mit den genannten Mitteln lässt sich auch erhöhte Temperatur und/oder verminderter Druck an wenden. Gegebenenfalls arbeitet man auch in Gegenwart indifferenter Gase. Statt aus Na- logenwasserstoffsäureestern direkt- Halogen wasserstoff abzuspalten, kann man das Ha logen auch in bekannter Weise durch einen quaternären Ammoniumrest ersetzen und diesen abspalten.
Das neue Verfahrensprodukt, das dll,1s_21- Acetoxy-pregnen-3,20-dion vom F.151-152 , soll therapeutische Verwendung finden oder als Zwischenprodukt zur Herstellung thera peutisch wertvoller Produkte dienen.
Beispiel: 1 Teil 12ss-Tosyloxy-21-acetoxy-pregnan- 3,20-dion (erhalten aus 3a,12,6-Dioxy-ätio- cholansäure vom F. 297 durch Acetylierung zur 3a,12,8 - Diacetoxy - ätiocholansäure vom F.
202-204 , Umsetzung zunächst mit Thio- nylchlorid, dann mit Diazomethan und nach folgende Verseifung zum 3a,12ss-Dioxy-21- diazo-pregnan-20-on, Überführung mittels Eisessig in 3a,12ss-Dioxy-21-acetoxy-pregnan- 20-on vom F. 149.5-150,5 , Oxydation mit tels Aluminiumphenolat und Aceton zum 12ss-Oxy-21-acetoxy-pregnan-3,20-diou, das schliesslich mit.
Tosylchlorid in Pyridin ver- estert wird) wird mit 20 Teilen Collidin 5 Stunden unter Rückfluss gekocht. Das Colli- din wird im Vakuum abdestilliert, der Rück stand in Äther aufgenommen, die ätherische Lösung mit verdünnter Salzsäure, Sodalösung und Wasser gewaschen, getrocknet und ein gedampft.
Das erhaltene gelbe Rohprodukt liefert bei der Chromatographie über 12 Teile Aluminiumoxyd und der Elution mit Benzol-Äther (9 :1) das dll.l2_21_Acetoxy- pregnen-3,20-dion der Formel
EMI0002.0040
in Form farbloser Prismen, die aus Äther- Petroläther umkristallisiert bei 151-152 schmelzen.
An Stelle von Collidin kann z. B. auch Pyridin verwendet werden.
Process for the preparation of a new compound of the Cyclopentanopolyhydr ophenanthren-R series. It has been found that a compound of the cyclopentanopolyhydrophenanthrene series which is unsaturated in the ring C can be obtained if. one a 21-acetoxy-pregnan- d, 20-dione,
which has a substituent which can be split off together with an adjacent hydrogen atom in the 12-position in ring C, treated with agents which split off these substituents to form a double bond.
The 12-position substituent of the starting material which can be split off together with an adjacent hydrogen atom can be a free hydroxyl group or a, for example, by carboxylic acids, such as acetic, propionic or benzoic acid, by sulfonic acid,
Hydrogen halide acids or xanthogenic acids esterified hydroxyl group.
The splitting off of this substituent with the formation of a double bond can take place with the means known per se for this reaction. For example, a free hydroxyl group can be removed under the action of mineral acids, preferably in solvents such as glacial acetic acid, alcohol, dioxane and the like, of phosphorus oxychloride, bisulfates, formic acid,
Oxalic acid, from acid anhydrides such as acetic anhydride or phosphorus pentoxide, or by the action of catalysts such as iodine or carboxylic acid salts, split off.
An esterified hydroxyl group is preferably also with alkalis in addition to the means mentioned. Alkaline earths, carbonates, organic bases such as pyridine, dimethylaniline, etc., split off.
Instead of or in combination with the agents mentioned, it is also possible to use increased temperature and / or reduced pressure. You may also work in the presence of inert gases. Instead of splitting off hydrogen halide directly from hydrofluoric acid esters, the halogen can also be replaced in a known manner by a quaternary ammonium radical and split off.
The new process product, the dll, 1s_21-acetoxy-pregnen-3,20-dione from F.151-152, is intended to find therapeutic use or serve as an intermediate in the manufacture of therapeutically valuable products.
Example: 1 part of 12ss-tosyloxy-21-acetoxy-pregnan- 3,20-dione (obtained from 3a, 12,6-dioxy-ethio-cholanic acid from F. 297 by acetylation to 3a, 12,8-diacetoxy-ethiocholanic acid from F.
202-204, reaction first with thionyl chloride, then with diazomethane and after subsequent saponification to give 3a, 12ss-dioxy-21-diazo-pregnan-20-one, conversion using glacial acetic acid into 3a, 12ss-dioxy-21-acetoxy-pregnane - 20-one from F. 149.5-150.5, oxidation with means of aluminum phenolate and acetone to 12ss-Oxy-21-acetoxy-pregnan-3,20-diou, which is finally with.
Tosyl chloride is esterified in pyridine) is refluxed with 20 parts of collidine for 5 hours. The collidin is distilled off in vacuo, the residue is taken up in ether, the ethereal solution is washed with dilute hydrochloric acid, soda solution and water, dried and evaporated.
Chromatography over 12 parts of aluminum oxide and elution with benzene ether (9: 1) gives the yellow crude product obtained the dll.l2_21_Acetoxypregnen-3,20-dione of the formula
EMI0002.0040
in the form of colorless prisms which, recrystallized from ether-petroleum ether, melt at 151-152.
Instead of collidine, for. B. pyridine can also be used.
Claims (1)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH245274T | 1941-03-21 | ||
CH240789T | 1942-01-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
CH245274A true CH245274A (en) | 1946-10-31 |
Family
ID=25728539
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CH245274D CH245274A (en) | 1941-03-21 | 1941-03-21 | Process for the preparation of a new compound of the cyclopentanopolyhydrophenanthrene series. |
Country Status (1)
Country | Link |
---|---|
CH (1) | CH245274A (en) |
-
1941
- 1941-03-21 CH CH245274D patent/CH245274A/en unknown
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