CH215569A - Process for the preparation of a pregnen-5-ol-3-one-20 derivative. - Google Patents
Process for the preparation of a pregnen-5-ol-3-one-20 derivative.Info
- Publication number
- CH215569A CH215569A CH215569DA CH215569A CH 215569 A CH215569 A CH 215569A CH 215569D A CH215569D A CH 215569DA CH 215569 A CH215569 A CH 215569A
- Authority
- CH
- Switzerland
- Prior art keywords
- pregnen
- derivative
- preparation
- diazo
- decomposition
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title description 4
- 239000002253 acid Substances 0.000 claims description 7
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical compound C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 claims description 4
- XXTZHYXQVWRADW-UHFFFAOYSA-N diazomethanone Chemical class [N]N=C=O XXTZHYXQVWRADW-UHFFFAOYSA-N 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- QRLVDLBMBULFAL-UHFFFAOYSA-N Digitonin Natural products CC1CCC2(OC1)OC3C(O)C4C5CCC6CC(OC7OC(CO)C(OC8OC(CO)C(O)C(OC9OCC(O)C(O)C9OC%10OC(CO)C(O)C(OC%11OC(CO)C(O)C(O)C%11O)C%10O)C8O)C(O)C7O)C(O)CC6(C)C5CCC4(C)C3C2C QRLVDLBMBULFAL-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- UVYVLBIGDKGWPX-KUAJCENISA-N digitonin Chemical compound O([C@@H]1[C@@H]([C@]2(CC[C@@H]3[C@@]4(C)C[C@@H](O)[C@H](O[C@H]5[C@@H]([C@@H](O)[C@@H](O[C@H]6[C@@H]([C@@H](O[C@H]7[C@@H]([C@@H](O)[C@H](O)CO7)O)[C@H](O)[C@@H](CO)O6)O[C@H]6[C@@H]([C@@H](O[C@H]7[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O7)O)[C@@H](O)[C@@H](CO)O6)O)[C@@H](CO)O5)O)C[C@@H]4CC[C@H]3[C@@H]2[C@@H]1O)C)[C@@H]1C)[C@]11CC[C@@H](C)CO1 UVYVLBIGDKGWPX-KUAJCENISA-N 0.000 claims description 2
- UVYVLBIGDKGWPX-UHFFFAOYSA-N digitonine Natural products CC1C(C2(CCC3C4(C)CC(O)C(OC5C(C(O)C(OC6C(C(OC7C(C(O)C(O)CO7)O)C(O)C(CO)O6)OC6C(C(OC7C(C(O)C(O)C(CO)O7)O)C(O)C(CO)O6)O)C(CO)O5)O)CC4CCC3C2C2O)C)C2OC11CCC(C)CO1 UVYVLBIGDKGWPX-UHFFFAOYSA-N 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000003814 drug Substances 0.000 claims 1
- 239000013067 intermediate product Substances 0.000 claims 1
- 239000000155 melt Substances 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SOADZZNUBPUHLR-UHFFFAOYSA-N 1,2,3,5,6-oxatetrazin-4-one Chemical compound O1N=NC(=O)N=N1 SOADZZNUBPUHLR-UHFFFAOYSA-N 0.000 description 1
- LUWROZHMGRPGKK-CYVXNRQHSA-N 2-diazo-1-[(8R,9S,10S,13S,14S)-3-hydroxy-10,13-dimethyl-2,3,4,5,6,7,8,9,11,12,14,15-dodecahydro-1H-cyclopenta[a]phenanthren-17-yl]ethanone Chemical compound [N+](=[N-])=CC(C1=CC[C@H]2[C@@H]3CCC4CC(CC[C@]4(C)[C@H]3CC[C@]12C)O)=O LUWROZHMGRPGKK-CYVXNRQHSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J7/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of two carbon atoms
-
- 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 Pregnen-6-ol-3-on-20-Derivates. Das Hauptpatent betrifft ein Verfahren zur Herstellung eines Pregnen-5-on-20-ol- derivates, welches dadurch gekennzeichnet ist, dass man Acetoxy-3-ätiocholen-5-säure in das entsprechende Säurehalogenid überführt, auf dieses überschüssiges Diazomethan einwirken lässt und aus dem Reaktionsgemisch das Diazo- 21-acetoxy-3-pregnen-5-on-20 abtrennt.
Gegenstand des vorliegenden Patentes ist ein Verfahren zur Herstellung des Diazo-21- pregnen-5-ol-3-on-20, welches dadurch gekenn zeichnet ist, dass man Acyloxy-3-ätiocholen- säure in das entsprechende Säurehalogenid überführt, auf dieses überschüssiges Diazo- methan einwirken lässt und das so erhaltene Acyloxy- 3 - diazo - 21- pregnen-5-on-20 darauf alkalisch verseift.
<I>Beispiel:</I> 1 g Acetoxy-3-ätiocholen-5-säure wird mit 5 cm' Benzen und 5 g reinstem Thionylchlo- rid 3 Stunden unter Rückfluss gekocht. Man dampft unter Feuchtigkeitsausschluss ein, wo bei das Chlorid bald kristallisiert. Es wird in 80 cms trockenem Äther gelöst und bei <B>-100</B> eine trockene ätherische Lösung von ca. 1-1,5g Diazomethan einlaufen gelassen.
Die Mischung lässt man einige Stunden bei <B>01,</B> dann noch 6 Stunden bei Zimmertempe ratur stehen, engt stark ein und gibt Petrol- äther zu bis zur Trübung. Das Diazoketon kristallisiert aus. Aus der Mutterlauge wer den weitere Mengen analog gewonnen. Ins gesamt erhält man so 0,7 g reines Produkt als schwach gelbliche Blättchen, die gegen <B>1500</B> (etwas verschieden je nach Heizge- schwindigkeit) unter lebhafter Zersetzung schmelzen.
Für die Herstellung des freien 21-Diazo- pregnen-3-ol-20-ons werden 1 g des obigen Acetates in 30 cm' Methanol suspendiert, mit 16 cm' einer 5prozentigen Lösung von Kaliumhydroxyd in Methanol versetzt und unter öfterem Umschwenken _ 6 Stunden bei Zimmertemperatur stehen gelassen. Die Kri stalle gehen dabei nach etwa einer halben Stunde in Lösung. Nach Zusatz von etwas Wasser wird im Vakuum stark eingeengt, wobei das Oxy-diazoketon auskristallisiert.
Es wird abgenutscht, mit Wasser gewaschen, im Vakuum getrocknet und aus Äther-Petrol- äther umkristallisiert, wodurch es in leicht gelblichen glänzenden Körnern erhalten wird, die bei 144 unter lebhafter Zersetzung schmel zen - bei langsamem Erhitzen kann der Smp. um mehrere Grade tiefer gefunden werden. Die Ausbeute ist fast quantitativ. Das Pro dukt gibt zum Unterschied gegenüber dem acetylierten Diazoketon mit Digitonin in 80- bis 90 prozentigem Alkohol eine Fällung.
Beim Lagern tritt allmählich Zersetzung ein.
Process for the preparation of a pregnen-6-ol-3-one-20 derivative. The main patent relates to a process for the production of a pregnen-5-one-20-ol derivative, which is characterized in that acetoxy-3-etiocholen-5-acid is converted into the corresponding acid halide, and excess diazomethane is allowed to act on this and then removed the diazo-21-acetoxy-3-pregnen-5-one-20 is separated from the reaction mixture.
The subject of the present patent is a process for the preparation of diazo-21-pregnen-5-ol-3-one-20, which is characterized in that acyloxy-3-ätiocholen- acid is converted into the corresponding acid halide, on this excess Diazomethane can act and the acyloxy-3-diazo-21-pregnen-5-one-20 obtained in this way is saponified in an alkaline manner.
<I> Example: </I> 1 g of acetoxy-3-etiocholen-5-acid is refluxed for 3 hours with 5 cm of benzene and 5 g of the purest thionyl chloride. It is evaporated with the exclusion of moisture, where the chloride soon crystallizes. It is dissolved in 80 cms of dry ether and, at <B> -100 </B>, a dry ethereal solution of approx. 1-1.5 g of diazomethane is run in.
The mixture is left to stand for a few hours at <B> 01, </B> then another 6 hours at room temperature, concentrated strongly and petroleum ether is added until it becomes cloudy. The diazoketone crystallizes out. From the mother liquor who the further amounts obtained analogously. In total, 0.7 g of pure product is obtained in the form of slightly yellowish flakes which melt towards <B> 1500 </B> (somewhat different depending on the heating speed) with vigorous decomposition.
For the preparation of the free 21-diazo-pregnen-3-ol-20-one, 1 g of the above acetate is suspended in 30 cm 'of methanol, 16 cm' of a 5 percent solution of potassium hydroxide in methanol are added and the mixture is swirled frequently for 6 hours left at room temperature. The crystals go into solution after about half an hour. After adding a little water, the mixture is concentrated strongly in vacuo, the oxydiazoketone crystallizing out.
It is suction filtered, washed with water, dried in vacuo and recrystallized from ether-petroleum ether, whereby it is obtained in slightly yellowish, shiny grains which melt at 144 with vigorous decomposition - with slow heating the melting point can be several degrees lower being found. The yield is almost quantitative. In contrast to the acetylated diazoketone with digitonin in 80 to 90 percent alcohol, the product is a precipitation.
Decomposition occurs gradually on storage.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH215569T | 1937-03-22 | ||
| CH212199T | 1937-03-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH215569A true CH215569A (en) | 1941-06-30 |
Family
ID=25725152
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH215569D CH215569A (en) | 1937-03-22 | 1937-03-22 | Process for the preparation of a pregnen-5-ol-3-one-20 derivative. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH215569A (en) |
-
1937
- 1937-03-22 CH CH215569D patent/CH215569A/en unknown
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