CH190644A - Process for the preparation of a keto-cyclopentano-dimethyl-tetradecahydro-phenanthrol. - Google Patents
Process for the preparation of a keto-cyclopentano-dimethyl-tetradecahydro-phenanthrol.Info
- Publication number
- CH190644A CH190644A CH190644DA CH190644A CH 190644 A CH190644 A CH 190644A CH 190644D A CH190644D A CH 190644DA CH 190644 A CH190644 A CH 190644A
- Authority
- CH
- Switzerland
- Prior art keywords
- water
- keto
- split
- dimethyl
- cyclopentano
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 11
- 238000002360 preparation method Methods 0.000 title description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 230000008030 elimination Effects 0.000 claims description 4
- 238000003379 elimination reaction Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 150000002902 organometallic compounds Chemical class 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 125000000468 ketone group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000000053 physical method Methods 0.000 claims description 2
- 150000003509 tertiary alcohols Chemical group 0.000 claims 2
- 150000003333 secondary alcohols Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000745 gonadal hormone Substances 0.000 description 1
- 239000003163 gonadal steroid hormone Substances 0.000 description 1
- 230000003054 hormonal effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- VXWPONVCMVLXBW-UHFFFAOYSA-M magnesium;carbanide;iodide Chemical compound [CH3-].[Mg+2].[I-] VXWPONVCMVLXBW-UHFFFAOYSA-M 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- WURFKUQACINBSI-UHFFFAOYSA-M ozonide Chemical compound [O]O[O-] WURFKUQACINBSI-UHFFFAOYSA-M 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Darstellung eines Keto-eyelopentano-dimethyl- tetr adekahydr o-phenanthrols. Gegenstand der vorliegenden Erfindung ist die Darstellung eines Keto-cyclopentano- dimethyl - tetradekahydro - phenanthrols aus einem Pregnauolon. Es ist dadurch gekenn zeichnet,
dass man allo-Pregnanol-3-on-20 durch Einwirkung metallorganischer Verbin dungen und anschliessende Zersetzung des gebildeten Anlagerungsproduktes in einen sekundär tertiären Di-Alkohol verwandelt, aus diesem Wasser abspaltet und die dabei erhaltene ungesättigte Verbindung durch Einwirkung von Oxydationsmitteln an der Kohlenstoff -Kohlenstoff -Doppelbin.dung un ter Ausbildung einer Ketongruppe spaltet.
Man kann die Wasserabspaltung vorteil haft durch physikalische Methoden, z. B. durch Erhitzen des Dialkohols im Hoch vakuum bewirken. Das gleiche Ergebnis kann aber auch mit chemischen Mitteln, z. B. durch Erhitzen des Dialkohols mit wasser freiem Kupfersulfat oder dergleichen erzielt werden. Als metallorganische Verbindung eignet sich vorzugsweise eine Magnesium-Organo- halogenverbindung, während man als Oxy dationsmittel vorzugsweise Ozon verwendet.
Das Verfahren ,gestattet, auf syntheti schem Wege, d. h. unabhängig von Harn und andern Ausgangsmaterialien, die das männ liche Sexualhormon enthalten, zu einem Pro dukt zu .gelangen, das zur Herstellung von Präparaten mit Keimdrüsenhormonwirkung 'Verwendung finden soll.
Das erhaltene Ketocyclopentanodimethyl- tetradekahydrophenanthrol, das sogenannte 3-Oxyätio-allo-cholanon-17, ist in der Lite ratur bereits beschrieben (vergleiche z. B. Helv. chim. acta, B. 17, 1934, S. 1,39,6). <I>Beispiel:
</I> Zu einer ätherischen Lösung von Methyl- magnesiumjodid, erhalten aus 4,28 g trocke nen. und entfetteten Magnesiumspänen, 11 cm' Methyljodid, 80 cm' trockenem Äther und einer Spur Jod werden langsam unter kräf tigem Rühren 2,8 g allo-Pregnanol-3-on-20 vom Schmelzpunkt 194' in 100 cm' trocke nem Äther gelöst zugegeben. Die Reaktions flüssigkeit wird während einer Stunde am Rückfluss-kühler zum Sieden erhitzt, worauf das Lösungsmittel abdestilliert und der Rückstand während etwa 3. Stunden im<B>Öl-</B> bad auf ungefähr 120 C erhitzt wird.
Nach dem Abkühlen wird Eis und verdünnte Salz säure (1 :5) zugegeben, um die Grignard- Verbindun.g zu zersetzen, und das Reaktions produkt mit Äther extrahiert. Der ätherische Extrakt wird zuerst gut mit Wasser, dann mit wässrigem Natriumthiosulfat und zu letzt wieder mit Wasser gewaschen, getrock net und verdampft. Der Rückstand stellt ein hellbraunes glasiges Produkt dar. Um die Abspaltung des Wassers aus .der Grignar.d- Verbindung zu vervollständigen, ist es ange zeigt, das Reaktionsprodukt im Hochvakuum während ca. 1 .Stunde unter Rückfluss auf 110 C zum Kochen zu erhitzen.
2,5 g des ungesättigten Alkohols der Formel C@2H:"EO werden in 2:50- cm' trocke nem Chloroform gelöst und die Lösung 3 Stunden unter Eiskühlung mit Ozon behan delt. Das Chloroform wird dann bei Zimmer temperatur im Vakuum abgedampft und der Rückstand, ein schwach gelbliches Harz, mit 50 cm' Eisessig während etwa 1 Stunde auf <B>50'</B> C erhitzt, wobei das Ozonid zersetzt wird. Die Eisessiglösung wird hierauf mit viel Wasser verdünnt, reit Äthererschöpfend extrahiert und die ätherische Lösung bis zur neutralen Reaktion mit Wasser ausge waschen.
Nach dem Trocknen der Lösung und Verdampfen des Äthers erhält man ein gelbliches Harz in einer Ausbeute von etwa 2,5 g. Durch Entfernung des bei der Ozoni- sierung entstandenen sauren Anteils durch Extraktion mit wässriger Alkalilösung erhält man ungefähr 1 g eines neutralen Produktes, das beim Umkristallisieren das 3-Oxy-ätio- allocholanon-17 der Formel C13H3p0. .vom Schmelzpunkt 174' C -ergibt.
Process for the preparation of a keto-eyelopentano-dimethyl-tetr adekahydr o-phenanthrols. The present invention relates to the preparation of a keto-cyclopentano-dimethyl-tetradecahydro-phenanthrol from a pregnauolone. It is characterized by
that allo-pregnanol-3-one-20 is converted into a secondary tertiary di-alcohol by the action of organometallic compounds and the subsequent decomposition of the addition product formed, and the water is split off from this water, and the unsaturated compound thus obtained is on the carbon-carbon by the action of oxidizing agents -Double bond under formation of a ketone group splits.
You can the elimination of water advantageous by physical methods, for. B. cause by heating the dialcohol in a high vacuum. The same result can also be achieved with chemical agents, e.g. B. can be achieved by heating the dialcohol with anhydrous copper sulfate or the like. A suitable organometallic compound is a magnesium-organo-halogen compound, while ozone is preferably used as the oxidizing agent.
The method allows synthetic routes, i.e. H. Regardless of urine and other raw materials that contain the male sex hormone, a product that is to be used in the manufacture of preparations with gonadal hormone effects is to be obtained.
The ketocyclopentanodimethyl-tetradecahydrophenanthrole obtained, the so-called 3-oxyätio-allo-cholanone-17, has already been described in the literature (compare, for example, Helv. Chim. Acta, B. 17, 1934, pp. 1,39,6 ). <I> example:
</I> To an ethereal solution of methyl magnesium iodide, obtained from 4.28 g dry. and defatted magnesium shavings, 11 cm 'methyl iodide, 80 cm' dry ether and a trace of iodine are slowly added, while stirring vigorously, 2.8 g of allo-pregnanol-3-one-20 with a melting point of 194 'dissolved in 100 cm' of dry ether . The reaction liquid is heated to boiling under the reflux condenser for one hour, whereupon the solvent is distilled off and the residue is heated to about 120 ° C. in an oil bath for about 3 hours.
After cooling, ice and dilute hydrochloric acid (1: 5) are added to decompose the Grignard compound, and the reaction product is extracted with ether. The ethereal extract is first washed thoroughly with water, then with aqueous sodium thiosulfate and finally again with water, dried and evaporated. The residue is a light brown glassy product. In order to complete the elimination of the water from the Grignar.d compound, it is indicated to reflux the reaction product to 110 ° C. for about 1 hour under high vacuum.
2.5 g of the unsaturated alcohol of the formula C @ 2H: "EO are dissolved in 2: 50 cm 'dry chloroform and the solution is treated with ozone for 3 hours while cooling with ice. The chloroform is then evaporated off in vacuo at room temperature and the residue, a pale yellowish resin, is heated with 50 cm 'glacial acetic acid for about 1 hour to <B> 50' </B> C, during which the ozonide is decomposed. The glacial acetic acid solution is then diluted with plenty of water, extracted with ether and the Wash out the essential solution with water until it becomes neutral.
After the solution has dried and the ether has evaporated, a yellowish resin is obtained in a yield of about 2.5 g. Removal of the acidic component formed during ozonization by extraction with aqueous alkali solution gives about 1 g of a neutral product which, when recrystallized, is 3-oxy-ethioallocholanone-17 of the formula C13H3p0. .from melting point 174 ° C.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE190644X | 1934-08-23 | ||
| CH188985T | 1934-12-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH190644A true CH190644A (en) | 1937-04-30 |
Family
ID=25721720
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH190644D CH190644A (en) | 1934-08-23 | 1935-08-21 | Process for the preparation of a keto-cyclopentano-dimethyl-tetradecahydro-phenanthrol. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH190644A (en) |
-
1935
- 1935-08-21 CH CH190644D patent/CH190644A/en unknown
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