CH236338A - Process for the preparation of 1,4-androstadien-ol-(17)-one-(3). - Google Patents
Process for the preparation of 1,4-androstadien-ol-(17)-one-(3).Info
- Publication number
- CH236338A CH236338A CH236338DA CH236338A CH 236338 A CH236338 A CH 236338A CH 236338D A CH236338D A CH 236338DA CH 236338 A CH236338 A CH 236338A
- Authority
- CH
- Switzerland
- Prior art keywords
- agent
- hydrogen
- hydrogen halide
- splitting
- androstadien
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 12
- 238000002360 preparation method Methods 0.000 title description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000012433 hydrogen halide Substances 0.000 claims description 6
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- HOPRXXXSABQWAV-UHFFFAOYSA-N anhydrous collidine Natural products CC1=CC=NC(C)=C1C HOPRXXXSABQWAV-UHFFFAOYSA-N 0.000 claims description 4
- UTBIMNXEDGNJFE-UHFFFAOYSA-N collidine Natural products CC1=CC=C(C)C(C)=N1 UTBIMNXEDGNJFE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 150000007530 organic bases Chemical class 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 230000001419 dependent effect Effects 0.000 claims 2
- 239000011230 binding agent Substances 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- MUMGGOZAMZWBJJ-DYKIIFRCSA-N Testostosterone Chemical compound O=C1CC[C@]2(C)[C@H]3CC[C@](C)([C@H](CC4)O)[C@@H]4[C@@H]3CCC2=C1 MUMGGOZAMZWBJJ-DYKIIFRCSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229960003604 testosterone Drugs 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
- 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
- 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)
Description
Verfahren zur Herstellung von d,,4 Androstadien-ol-(17)-on-(3). Gegenstand des vorliegenden Patentes ist ein Verfahren zur Herstellung von dl,g-An- drostadien-ol-(17)-on-(3), das dadurch ge kennzeichnet ist, dass man 2,4-Dihalogen- androstanol-(17)-on-(3) mit einem Halogen wasserstoff abspaltenden Mittel behandelt.
Die neue Verbindung soll als Arzneimittel sowie als Zwischenprodukt für die Herstel lung von Arzneimitteln Verwendung finden.
Für die Halogenwasserstoffabspaltung eignen sich Mittel, die zum Teil bereits in dem Hauptpatent genannt sind, z. B. Am moniak oder organische Basen, insbesondere heterocyklische Basen, wie Pyridin, Piperidin und Chinolin, weiter aliphatische oder aro matische Amine, wie Dimethylanilin, Dime- thylamin u. a. Als besonders zweckmässig hat sich die Verwendung von Collidin erwiesen, durch welche das Verfahrensprodukt in be sonders guter Ausbeute erhalten wird.
Die Behandlung wird beispielsweise mit zweckmässig wasserfreien Basen, gegebenen falls in-Gegenwart eines geeigneten Lösungs- mittels, in der Weise durchgeführt, dass man die Ausgangsstoffe mit den Basen erwärmt bezw. am Rückflusskühler kocht.
Durch Zusatz von Stoffen, welche die ab gespaltenen Halogenwasserstoffsäuren zu binden vermögen, ohne dass sie mit dem Aus gangsmaterial in Reaktion treten, z. B. von galziumcarbonat, Natriumcarbonat und dergl., kann der isomerisierende und verharzende Einfluss der gegebenenfalls vorhandenen freien Halogenwasserstoffsäuren zurück gedrängt werden.
Beispiel: 10 g 2,4-Dibrom-androstanol-(17)-on-(3) werden in 125 cm' Collidin 3/4 Stunden ge kocht. Nach dem Erkalten wird die Lösung mit Äther verdünnt, vom Collidinsalz abde- kantiert und mit verdünnter Schwefelsäure, Sodalösung und Wasser gewaschen. Die neu trale ätherische Lösung wird über Natrium sulfat getrocknet und eingedampft.
Der braune Rückstand wird aus einer Lösung in einem Benzol-Benzin-Gemisch 1 : 1 an Alu- miniumogyd (Merck stand. nach Brockmann) absorbiert. Aus dem Eluat mittels des glei chen Gemisches gelingt es, nach Verdampfen des Lösungsmittels das Al,.4-Androstadien-ol- (17)-on-(3) zu erhalten, das nach Umkristalli- sieren aus wässrigem Methanol feine Nadeln vom Schmelzpunkt 168-169 bildet. Die Ausbeute beträgt 3 g. Im Kapaunenkammtest ist es stärker wirksam als Testosteron.
Process for the preparation of d ,, 4 androstadien-ol- (17) -one- (3). The subject of the present patent is a process for the preparation of dl, g-androstadien-ol- (17) -one- (3), which is characterized in that 2,4-dihalogeno- androstanol- (17) - on- (3) treated with a hydrogen splitting agent.
The new compound is to be used as a drug and as an intermediate for the manufacture of drugs.
For the elimination of hydrogen halide agents are suitable, some of which are already mentioned in the main patent, e.g. B. Am moniak or organic bases, especially heterocyclic bases such as pyridine, piperidine and quinoline, further aliphatic or aromatic amines such as dimethylaniline, dimethylamine and the like. a. The use of collidine has proven to be particularly useful, by means of which the process product is obtained in particularly good yield.
The treatment is carried out, for example, with expedient anhydrous bases, if appropriate in the presence of a suitable solvent, in such a way that the starting materials are heated or respectively with the bases. boils on the reflux condenser.
By adding substances that are able to bind the split hydrohalic acids without having to react with the starting material, for. B. of calcium carbonate, sodium carbonate and the like., The isomerizing and resinifying influence of any free hydrohalic acids can be suppressed.
Example: 10 g of 2,4-dibromo-androstanol- (17) -one- (3) are boiled in 125 cm 'collidine for 3/4 hours. After cooling, the solution is diluted with ether, decanted from the collidine salt and washed with dilute sulfuric acid, soda solution and water. The neutral ethereal solution is dried over sodium sulfate and evaporated.
The brown residue is absorbed from a solution in a 1: 1 benzene-gasoline mixture of aluminum yogide (Merck stand. According to Brockmann). From the eluate by means of the same mixture it is possible, after evaporation of the solvent, to obtain the Al, .4-androstadien-ol- (17) -one- (3), which after recrystallization from aqueous methanol, fine needles with a melting point of 168 -169 forms. The yield is 3 g. In the capon comb test, it is more effective than testosterone.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH201947T | 1937-05-27 | ||
| DE236338X | 1940-02-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH236338A true CH236338A (en) | 1945-01-31 |
Family
ID=25723749
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH236338D CH236338A (en) | 1937-05-27 | 1941-01-31 | Process for the preparation of 1,4-androstadien-ol-(17)-one-(3). |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH236338A (en) |
-
1941
- 1941-01-31 CH CH236338D patent/CH236338A/en unknown
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