CH210774A - Process for the preparation of an oxyketone ester of the androstane series. - Google Patents
Process for the preparation of an oxyketone ester of the androstane series.Info
- Publication number
- CH210774A CH210774A CH210774DA CH210774A CH 210774 A CH210774 A CH 210774A CH 210774D A CH210774D A CH 210774DA CH 210774 A CH210774 A CH 210774A
- Authority
- CH
- Switzerland
- Prior art keywords
- oxidizing agent
- preparation
- ester
- oxyketone
- benzoate
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 8
- 150000001441 androstanes Chemical class 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title claims description 4
- -1 oxyketone ester Chemical class 0.000 title description 5
- 239000007800 oxidant agent Substances 0.000 claims description 6
- DJTOLSNIKJIDFF-LOVVWNRFSA-N 5alpha-Androstan-3beta-ol Chemical compound C([C@@H]1CC2)[C@@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CCC[C@@]2(C)CC1 DJTOLSNIKJIDFF-LOVVWNRFSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005751 Copper oxide Substances 0.000 claims description 3
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910000431 copper oxide Inorganic materials 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 238000002560 therapeutic procedure Methods 0.000 claims description 2
- 238000003776 cleavage reaction Methods 0.000 claims 1
- 230000007017 scission Effects 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- HAMNKKUPIHEESI-UHFFFAOYSA-N aminoguanidine Chemical compound NNC(N)=N HAMNKKUPIHEESI-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical class [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000004031 phenylhydrazines Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide Chemical compound NNC(N)=O DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- 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)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
Description
Verfahren zur Darstellung eines Ogyketonesters der Androstanreihe. Es wurde gefunden, dass man zu einem Oxyketonester der Androstanreihe gelangen kann, wenn man auf ein Androetandiol- (3',17)-17-benzoat der Formel
EMI0001.0008
ein Oxydationsmittel einwirken lässt.
Das so gewonnene Androstanol-(17)-on- (3)-benzoat der Formel
EMI0001.0011
bildet farblose Kristalle vom F. 200-2010. Wie Versuche ergaben, gelingt es leicht,
den entstandenen Oxyketonesster entweder durch direkte Kristallisation oder durch Be reitung schwer löslicher Derivate in reiner Form abzuscheiden. Solche schwer lösliche Derivate erhält man zum 'Beispiel durch Umsetzung mit den üblichen Ketonreagen- zien wie Semicarbazid, Thiasemicarbazid, $ydroxylamin, Aminoguanidin, Phenyl- hydrazinen,
neutralen oder basischen Acyl- hydraziden. Durch Einwirkung hydrolytisch wirkender Mittel werden die zwecks Reini gung des Oxyketonesters hergestellten Ver bindungen wieder in ihre Komponenten .ge spalten.
Geeignete Oxydationsmittel sind zum Beispiel 6-wertige Chromverbindungen wie Chrom=säure in Eisessig, ferner Kupferoxyd, Permanganate und dergleichen.
Die erhaltene Verbindung soll therapeu tische Verwendung finden. <I>Beispiel:</I> 2,5 g Androstan-3-eis-17-trans-diol-17- monobenzoat vom F. 203-204' werden in 100 em3 Eisessig gelöst und mit einer Lösung von 0,63 g Chromtrioxyd in 63 cm'' Eisessig versetzt. Nach Stehen über Nacht bei Zimmertemperatur verdünnt man mit Wasser, nimmt das Reaktionsprodukt in Äther auf, wäscht die Atherlösung und engt sie ein, wobei Kristallisation erfolgt.
Durch Umkristallisieren aus Benzin-Essigester er hält man .das bei 200-2011 schmelzende Androstanol-(17)-on-(3)-benzoat, das sieh zum Beispiel auch über das schwer lösliche Semicarba.zon isolieren und reinigen lässt.
Statt von der 3-cis-Verbindung kann man ebensogut von :der 3-trans-Verbindung aus gehen.
An Stelle von Chromeäure kann zur Oxy dation zum Beispiel auch Kupferoxyd Ver wendung finden.
Process for the preparation of an ogyketone ester of the androstane series. It has been found that an oxyketone ester of the androstane series can be obtained by using an androetanediol (3 ', 17) -17-benzoate of the formula
EMI0001.0008
allows an oxidizing agent to act.
The androstanol (17) one (3) benzoate of the formula obtained in this way
EMI0001.0011
forms colorless crystals from F. 200-2010. As experiments have shown, it is easy to
to deposit the resulting Oxyketonesster either by direct crystallization or by Be preparation of poorly soluble derivatives in pure form. Such poorly soluble derivatives are obtained, for example, by reaction with the usual ketone reagents such as semicarbazide, thiasemicarbazide, hydroxylamine, aminoguanidine, phenylhydrazines,
neutral or basic acyl hydrazides. By the action of hydrolytic agents, the compounds produced for the purpose of cleaning the oxyketone ester are split back into their components.
Suitable oxidizing agents are, for example, hexavalent chromium compounds such as chromic acid in glacial acetic acid, as well as copper oxide, permanganates and the like.
The compound obtained is intended to be used in therapy. <I> Example: </I> 2.5 g of androstane-3-cis-17-trans-diol-17-monobenzoate of F. 203-204 'are dissolved in 100 cubic meters of glacial acetic acid and mixed with a solution of 0.63 g Chromium trioxide in 63 cm '' glacial acetic acid added. After standing overnight at room temperature, it is diluted with water, the reaction product is taken up in ether, the ether solution is washed and concentrated, with crystallization taking place.
Recrystallization from petrol ethyl acetate gives the androstanol- (17) -one- (3) -benzoate, which melts at 200-2011 and which can also be isolated and purified via the sparingly soluble semicarba.zone, for example.
Instead of the 3-cis connection, one can just as well start from: the 3-trans connection.
Instead of chromic acid, for example, copper oxide can also be used for oxidation.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH208082T | 1935-06-18 | ||
| CH210774T | 1935-06-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH210774A true CH210774A (en) | 1940-07-31 |
Family
ID=25724492
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH210774D CH210774A (en) | 1935-06-18 | 1935-06-18 | Process for the preparation of an oxyketone ester of the androstane series. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH210774A (en) |
-
1935
- 1935-06-18 CH CH210774D patent/CH210774A/en unknown
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