CH211653A - Process for the preparation of a ring ketone of the cyclopentanopolyhydrophenanthrene series. - Google Patents
Process for the preparation of a ring ketone of the cyclopentanopolyhydrophenanthrene series.Info
- Publication number
- CH211653A CH211653A CH211653DA CH211653A CH 211653 A CH211653 A CH 211653A CH 211653D A CH211653D A CH 211653DA CH 211653 A CH211653 A CH 211653A
- Authority
- CH
- Switzerland
- Prior art keywords
- preparation
- ring
- ring ketone
- series
- cyclopentanopolyhydrophenanthrene series
- Prior art date
Links
- 150000002576 ketones Chemical class 0.000 title claims description 6
- 238000000034 method Methods 0.000 title claims description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 3
- 125000000468 ketone group Chemical group 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229930194542 Keto Natural products 0.000 claims 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 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 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 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
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- -1 magnesium halogen Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture 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
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical group [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-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)
- Steroid Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
Verfahren zur Darstellung eines Ringbetons der Cyelopentanopolyhydro- phenanthren-Reihe. Es wurde gefunden; dass man zu einem Ringketon der Cyclopentanopolybydrophen- anthren-Reihe gelangen kann, wenn man d'4- 17-Äthinyl-androstendiol-(3,17) mit Mitteln behandelt, die geeignet sind, die freie sekun däre Ringcarbinolgruppe in eine Ketogruppe überzuführen und die vorhandene boppelbin- dung in 4,5-Stellung zu verschieben.
Das so gewonnene d', -17-Äthinyl-testo- steron der Formel
EMI0001.0015
schmilzt bei 270-2720.
Die Überführung der freien Ringcarbinol- in die Ringketogruppe kann mit für solche Reaktionen bekannterweise verwendbaren Mitteln erfolgen, beispielsweise mit Chrom säure und Eisessig, mit Permanganat und dergleichen. Es können aber auch Carbonyl- verbindungen (beispielsweise Ketone wie Ace ton, Cyclohexanon) in Gegenwart von Metall- alkoholaten (z.
B. Aluminiumbutylaten, -pro- pylaten, Magnesium-halogen-alkoholaten), Me talle oder Metalloxyde der Kupfer-, Eisen- oder Platingruppe, gegebenenfalls unter ver mindertem Druck, in Gegenwart inerter Gase und/oder in Kombination mit Wasserstoff- acceptoren, verwendet werden.
Es wurde gefunden, dass überraschender weise ein Schutz der mehrfachen Kohlenatoff- Kohlenatoff-bindung in der Seitenkette unter den für solche Oxydationen üblichen milden Bedingungen völlig überflüssig ist. Wird die Reaktion in neutraler Lösung ausgeführt, so wird vorerst das P.r-ungesättigte Keton er halten. Dieses wird nachträglich durch saure oder basische Mittel ebenfalls in das a.p- ungesättigte Keton umgelagert.
Die neue Verbindung soll therapeutische Verwendung finden, oder als Zwischenprodukt zur Herstellung therapeutisch vervWrdbarer Stoffe dienen.
<I>" Beispiel:</I> 0,5 Teile d',E-17-Äthinyl-androstendiol- (3,17) werden in 10 Teile trockenem Aceton gelöst, mit einer Lösung von 1 Teil tertiärem Aluminium-butylat in 40 Teilen absolutem Toluol versetzt und 21 Stunden unter Rück fluss gekocht. Nach dem Abkühlen verdünnt man mit 100 Teilen Äther, wäscht die Lö sung mit verdünnter Mineralsäure und Wasser, trocknet sie und verdampft das Lösungsmittel. Man erhält so dr,'-17-Äthinyl-andr-osten-3-on- 17-ol vom F. 270-272', welches sich aus Essigester umkristallisieren lässt.
Process for the production of a ring concrete of the Cyelopentanopolyhydro- phenanthrene series. It was found; that one can get to a ring ketone of the Cyclopentanopolybydrophen- anthrene series if one treats d'4- 17-Äthynyl-androstendiol- (3,17) with agents which are suitable for converting the free secondary ring carbinol group into a keto group and to move the existing double binding to the 4.5 position.
The thus obtained d ', -17-ethynyl testosterone of the formula
EMI0001.0015
melts at 270-2720.
The free ring carbinol group can be converted into the ring keto group with agents known to be useful for such reactions, for example with chromic acid and glacial acetic acid, with permanganate and the like. However, carbonyl compounds (for example ketones such as acetone, cyclohexanone) can also be used in the presence of metal alcoholates (e.g.
B. aluminum butylates, propylates, magnesium halogen alcoholates), metals or metal oxides of the copper, iron or platinum group, optionally under reduced pressure, in the presence of inert gases and / or in combination with hydrogen acceptors will.
It has been found that, surprisingly, protection of the multiple carbon-carbon bond in the side chain is completely superfluous under the mild conditions customary for such oxidations. If the reaction is carried out in neutral solution, the P.r-unsaturated ketone will first be kept. This is also subsequently rearranged into the a.p- unsaturated ketone by acidic or basic agents.
The new compound should find therapeutic use or serve as an intermediate product for the production of therapeutically useful substances.
<I> "Example: </I> 0.5 part of d ', E-17-ethynyl-androstenediol- (3.17) are dissolved in 10 parts of dry acetone, with a solution of 1 part of tertiary aluminum butoxide in 40 Parts of absolute toluene are added and the mixture is refluxed for 21 hours. After cooling, it is diluted with 100 parts of ether, the solution is washed with dilute mineral acid and water, dried and the solvent is evaporated. This gives dr, '- 17-ethynyl- andr-osten-3-on-17-ol from F. 270-272 ', which can be recrystallized from ethyl acetate.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH211653T | 1937-07-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH211653A true CH211653A (en) | 1940-10-15 |
Family
ID=4447436
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH211653D CH211653A (en) | 1937-07-22 | 1937-07-22 | Process for the preparation of a ring ketone of the cyclopentanopolyhydrophenanthrene series. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH211653A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2721871A (en) * | 1954-09-13 | 1955-10-25 | Searle & Co | 17-alkyl derivatives of 19-nortestosterone |
| US2744122A (en) * | 1951-11-22 | 1956-05-01 | Syntex Sa | delta 4-19-nor-17alpha-ethinylandrosten-17beta-ol-3-one and process |
| US2774777A (en) * | 1952-11-12 | 1956-12-18 | Syntex Sa | 17alpha-methyl-19-nortesterone |
-
1937
- 1937-07-22 CH CH211653D patent/CH211653A/en unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2744122A (en) * | 1951-11-22 | 1956-05-01 | Syntex Sa | delta 4-19-nor-17alpha-ethinylandrosten-17beta-ol-3-one and process |
| US2774777A (en) * | 1952-11-12 | 1956-12-18 | Syntex Sa | 17alpha-methyl-19-nortesterone |
| US2721871A (en) * | 1954-09-13 | 1955-10-25 | Searle & Co | 17-alkyl derivatives of 19-nortestosterone |
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