CH295249A - Process for the preparation of a new ester. - Google Patents
Process for the preparation of a new ester.Info
- Publication number
- CH295249A CH295249A CH295249DA CH295249A CH 295249 A CH295249 A CH 295249A CH 295249D A CH295249D A CH 295249DA CH 295249 A CH295249 A CH 295249A
- Authority
- CH
- Switzerland
- Prior art keywords
- preparation
- new ester
- parts
- volume
- double bond
- Prior art date
Links
Classifications
-
- 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 neuen Esters. Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung des Trimethyl- acetats von Desoxycorticosteron.
Der neue Ester wird erhalten, wenn man auf d5-3-Oxy-@20-keto-21-trimethylacetoxy- prebnen ein Oxydationsmittel einwirken lässt und die Doppelbindung in 4,5-Stellung ver schiebt. Das Verfahrensprodukt, das Desoxy- eorticosteron-trimethylacetat (Z14-3,20-Diketo- 21- trimethylacetoxy - pregnen), schmilzt bei 199-200 . Es soll als Heilmittel verwendet werden.
Zur Oxydation können die verschieden sten chemischen oder biochemischen Oxyda- tionsmethoden verwendet werden. Man kann beispielsweise mit Hilfe von Verbindungen des 6wertigen Chroms, z. B. Chromsäure in Lösungsmitteln, wie Eisessig, oxydieren, wo bei die Doppelbindung vorzugsweise vorüber gehend durch Anlagerung von Halogen ge schützt wird.
Besonders geeignet ist die Me thode nach Oppenauer, das heisst Verwen dung eines Ketons, wie .Cyclohexanon, in Ge genwart eines Alkoholau oder Phenolats, wie Aluminium-isopropylat oder Aluminium- phenolat. Bei der letzteren Methode wird die Doppelbindung unter der Einwirkung des Alkoholau oder Phenolats schon während der Oxydation verschoben. Wird hingegen die Doppelbindung während der Oxydation vor übergehend, z.
B. durch Bromaddition, ge schützt, so muss die Verschiebung nachträg lich, z. B. durch Einwirkung von sauren oder basischen Katalysatoren, vorgenommen wer- den. Dies geschieht meist schon beim Ent- halogenieren, insbesondere durch Einwir kung von Zink und Eisessig.
Beispiel <I>1:</I> 2 Gewichtsteile d5-3fl-Oxy-20-keto-21-tri- methylacetoxy-pregnen werden in 100 Volum- teilen Toluol gelöst, 10 Volumteile frisch destilliertes Cyclohexanon zugegeben und zur siedenden Lösung innert 15 Minuten eine Lö sung von 3,
5 Gewichtsteilen Aluminium-isopro- pylat in 20 Volumteilen Toluol zugeführt. Das Gemisch wird dann 4 Stunden am Rück fluss gekocht, mit 5 Volumteilen Eisessig ver setzt und während 2 Stunden mit Wasser dampf destilliert.
Das ausgeschiedene feste Rohprodukt wird in einem Gemisch aus 150 V olumteilen Äther und 50 Volumteilen Chloroform aufgenommen und die organische Lösung mit Wasser, verdünnter Bicarbonat- lösimg und Wasser gewaschen. Nach dem Trocknen und Eindampfen erhält man ein Rohprodukt,
aus dem durch Kristallisation aus einem Gemisch von Benzol leid Isopropyl- äther das Desoxycortieosteron-trimethylacetat der Formel
EMI0001.0077
vom F. = 199-200 C ( [a] = + 176 , D c = 1,035 in Chloroform) gewonnen wird.
Process for the preparation of a new ester. The present invention relates to a process for the preparation of the trimethyl acetate of deoxycorticosterone.
The new ester is obtained if an oxidizing agent is allowed to act on d5-3-Oxy- @ 20-keto-21-trimethylacetoxyprebnen and the double bond is shifted to the 4,5-position. The product of the process, deoxy-eorticosterone-trimethylacetate (Z14-3,20-diketo-21-trimethylacetoxy - pregnen), melts at 199-200. It is said to be used as a remedy.
Various chemical or biochemical oxidation methods can be used for the oxidation. You can for example with the help of compounds of 6-valent chromium, z. B. chromic acid in solvents such as glacial acetic acid, where the double bond is preferably protected temporarily ge by the addition of halogen.
The Oppenauer method is particularly suitable, that is to say using a ketone such as cyclohexanone in the presence of an alcohol or phenolate such as aluminum isopropoxide or aluminum phenolate. In the latter method, the double bond is displaced under the action of the alcohol or phenolate during the oxidation. If, however, the double bond is transient during the oxidation, z.
B. by bromine addition, ge protected, the shift must subsequently Lich, z. B. by the action of acidic or basic catalysts can be made. This usually takes place during the de-halogenation, in particular when zinc and glacial acetic acid act.
Example <I> 1: </I> 2 parts by weight of d5-3fl-oxy-20-keto-21-trimethylacetoxy-pregnen are dissolved in 100 parts by volume of toluene, 10 parts by volume of freshly distilled cyclohexanone are added and added to the boiling solution within 15 Minutes a solution of 3,
5 parts by weight of aluminum isopropylate in 20 parts by volume of toluene are supplied. The mixture is then refluxed for 4 hours, ver with 5 parts by volume of glacial acetic acid and steam distilled for 2 hours.
The precipitated solid crude product is taken up in a mixture of 150 parts by volume of ether and 50 parts by volume of chloroform and the organic solution is washed with water, dilute bicarbonate solution and water. After drying and evaporation, a crude product is obtained
from which by crystallization from a mixture of benzene sorry isopropyl ether the deoxycortieosterone trimethylacetate of the formula
EMI0001.0077
from m.p. = 199-200 C ([a] = + 176, D c = 1.035 in chloroform).
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH295249T | 1950-03-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH295249A true CH295249A (en) | 1953-12-15 |
Family
ID=4488819
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH295249D CH295249A (en) | 1950-03-24 | 1950-03-24 | Process for the preparation of a new ester. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH295249A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024147726A1 (en) * | 2023-01-05 | 2024-07-11 | Interquim S.A. De C.V | Synthesis of desoxycorticosterone pivalate |
-
1950
- 1950-03-24 CH CH295249D patent/CH295249A/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024147726A1 (en) * | 2023-01-05 | 2024-07-11 | Interquim S.A. De C.V | Synthesis of desoxycorticosterone pivalate |
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