CH210760A - Process for the preparation of an oxyketone of the androstane series. - Google Patents
Process for the preparation of an oxyketone of the androstane series.Info
- Publication number
- CH210760A CH210760A CH210760DA CH210760A CH 210760 A CH210760 A CH 210760A CH 210760D A CH210760D A CH 210760DA CH 210760 A CH210760 A CH 210760A
- Authority
- CH
- Switzerland
- Prior art keywords
- trans
- oxidizing agent
- process according
- oxyketone
- androstandiol
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims description 6
- 150000001441 androstanes Chemical class 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title claims 2
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 6
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 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
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 210000001625 seminal vesicle Anatomy 0.000 claims description 2
- 230000001225 therapeutic effect Effects 0.000 claims description 2
- 201000010653 vesiculitis Diseases 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims 5
- 238000003776 cleavage reaction Methods 0.000 claims 2
- 230000003301 hydrolyzing effect Effects 0.000 claims 2
- 230000007017 scission Effects 0.000 claims 2
- 239000007858 starting material Substances 0.000 claims 2
- 238000000354 decomposition reaction Methods 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- HAMNKKUPIHEESI-UHFFFAOYSA-N aminoguanidine Chemical compound NNC(N)=N HAMNKKUPIHEESI-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical class [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- -1 e.g. B. the acetate Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000004031 phenylhydrazines Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-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)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Steroid Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfuhren zur Darstellung eines Ogyketons der Androstanreihe. Es wurde gefunden, @dass man zu einem Oxyketon der Androstanreihe gelangen kann; wenn man auf ein in 17-Stellung verestertes 17-trans-Androstandiol-($,17) der Formel
EMI0001.0009
ein Oxydationsmittel einwirken lässt und die so - erhaltene Verbindung verseift.
Das so gewonnene Androstan-trans-ol- (17)-on-(3) der Formel
EMI0001.0012
bildet farblose Kristalle vom F. 182 . Wie Versuche ergaben, gelingt es leicht, das entstehende Oxyketon entweder durch direkte Kristallisation oder durch Bereitung schwer löslicher Derivate in reiner Form ab- zuscheiden.Solche schwer lösliche Derivate erhält man zum Beispiel durch <RTI
ID="0001.0025"> Umsetzung des Oxyketons mit den üblichen Keton- reagenzien wie @Semicarbazid, Thiosemi- carbazid, Hydroxylamin, Aminoguanidin, Phenylhydrazinen, neutralen oder basischen Acylhydrazinen. Zur Reinigung und Tren nung erwies sich auch die Acylierung mit Acylierungsmitteln wie Acetanhydrid, Ben- zoylchlorid,
Dinätrobenzoylchlorid als vorteil haft. Durch Einwirkung hydrolytisch wir kender Mittel werden .die zwecks Reinigung des Oxyketons hergestellten Verbindungen wieder in ihre Komponenten gespalten.
Geeignete Oxydationsmittel sind zum Beispiel 6wertige Chromverbindungen wie Chromsäure in Eisessig, ferner Kupferoxyd, Permanganat und dergleichen.
Die erhaltene Verbindung zeichnet sich durch hohe Wirksamkeit am Kapaunenkamni und an der Samenblase aus. Sie soll thera peutische Verwendung finden.
Beispiel: 2,01 g Androstan-3-traiis-l.7-tranz,-diol-17- hexahydrobenzoat vom F. 167-168' werden in 30 cm' Eisessig gelöst und mit einer Lö sung von 0,50g Chromsäure in 7,5 ein' 90'i,-;er Essigsäure versetzt. Nach dem Stehen über Nacht bei Zimmertemperatur wird mit Wasser gefällt, filtriert, gewaschen und getrocknet.
Das so erhaltene Androstan- 2-on-17-trans-ol-hexahydrobenzoa.t schmilzt bei<B>161-166'.</B> Zur Verseifung werden 4 g davon mit ?5 cm' Methylalkohol und 25 cm' normaler methylalkoholischer Natronlauge 2 Stunden am Rückfluss gekocht. Das Andro- stan-3-on-17-trans-ol wird mit Wasser aus gefällt und nach dem Trocknen aus Essig ester umkristallisiert. Es schmilzt bei<B>182'.</B>
An Stelle des Hexahydrobenzoateskönnen auch andere Ester, wie z. B. das Acetat, das Propionat, ein Butyrat, ein Valerianat, das Benzoat, oder auch Ester anorganischer Säuren, wie der 11alogen-Wasserstoffsäuren, Verwendung finden.
Statt von den 3-trans-Verbindungen kann man ebensogut von den 3-cis-Verbindungen ausgehen.
Method of representing an ogyketone of the androstane series. It was found that an oxyketone of the androstane series can be obtained; when looking at a 17-trans-androstandiol esterified in the 17-position - ($, 17) of the formula
EMI0001.0009
allows an oxidizing agent to act and saponifies the compound thus obtained.
The androstane-trans-ol- (17) -one- (3) of the formula obtained in this way
EMI0001.0012
forms colorless crystals of F. 182. Experiments have shown that it is easy to separate the resulting oxyketone either by direct crystallization or by preparing poorly soluble derivatives in pure form. Such poorly soluble derivatives are obtained, for example, by <RTI
ID = "0001.0025"> Reaction of the oxyketone with the usual ketone reagents such as @Semicarbazid, Thiosemicarbazid, hydroxylamine, aminoguanidine, phenylhydrazines, neutral or basic acylhydrazines. The acylation with acylating agents such as acetic anhydride, benzoyl chloride,
Dinätrobenzoylchlorid as advantageous. By the action of hydrolytically active agents, the compounds produced for the purpose of cleaning the oxyketone are split back into their components.
Suitable oxidizing agents are, for example, hexavalent chromium compounds such as chromic acid in glacial acetic acid, also copper oxide, permanganate and the like.
The compound obtained is characterized by its high effectiveness on the Kapaunenkamni and the seminal vesicle. It should find therapeutic use.
Example: 2.01 g of androstane-3-traiis-1.7-tranz, -diol-17-hexahydrobenzoate of F. 167-168 'are dissolved in 30 cm' of glacial acetic acid and mixed with a solution of 0.50 g of chromic acid in 7 , 5 a '90'i, -; he added acetic acid. After standing overnight at room temperature, it is precipitated with water, filtered, washed and dried.
The androstan-2-one-17-trans-ol-hexahydrobenzoa.t thus obtained melts at <B> 161-166 '. </B> For saponification, 4 g of it are mixed with? 5 cm? Methyl alcohol and 25 cm? Normal methyl alcohol Sodium hydroxide solution boiled under reflux for 2 hours. The androstan-3-one-17-trans-ol is precipitated with water and, after drying, recrystallized from ethyl acetate. It melts at <B> 182 '. </B>
Instead of the hexahydrobenzoate, other esters, such as e.g. B. the acetate, the propionate, a butyrate, a valerianate, the benzoate, or esters of inorganic acids, such as the 11alohydrogenic acids, are used.
Instead of the 3-trans compounds, one can just as easily start from the 3-cis compounds.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH208082T | 1935-06-18 | ||
| CH210760T | 1935-06-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH210760A true CH210760A (en) | 1940-07-31 |
Family
ID=25724478
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH210760D CH210760A (en) | 1935-06-18 | 1935-06-18 | Process for the preparation of an oxyketone of the androstane series. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH210760A (en) |
-
1935
- 1935-06-18 CH CH210760D patent/CH210760A/en unknown
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