CH192062A - Process for the preparation of an unsaturated alcohol. - Google Patents
Process for the preparation of an unsaturated alcohol.Info
- Publication number
- CH192062A CH192062A CH192062DA CH192062A CH 192062 A CH192062 A CH 192062A CH 192062D A CH192062D A CH 192062DA CH 192062 A CH192062 A CH 192062A
- Authority
- CH
- Switzerland
- Prior art keywords
- hydrogen
- preparation
- reducing agent
- alcohol
- metal catalysts
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 12
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 title claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 229910000510 noble metal Inorganic materials 0.000 claims description 3
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 claims description 3
- 229910003446 platinum oxide Inorganic materials 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 230000001225 therapeutic effect Effects 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims 2
- 150000001298 alcohols Chemical class 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical class O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- -1 magnesium alkyl halides Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- CBMYJHIOYJEBSB-YSZCXEEOSA-N 5alpha-androstane-3beta,17beta-diol Chemical compound C1[C@@H](O)CC[C@]2(C)[C@H]3CC[C@](C)([C@H](CC4)O)[C@@H]4[C@@H]3CC[C@H]21 CBMYJHIOYJEBSB-YSZCXEEOSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 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
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- FMGSKLZLMKYGDP-USOAJAOKSA-N dehydroepiandrosterone Chemical compound C1[C@@H](O)CC[C@]2(C)[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CC=C21 FMGSKLZLMKYGDP-USOAJAOKSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 229960002847 prasterone Drugs 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 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
- C07J1/0003—Androstane derivatives
- C07J1/0018—Androstane derivatives substituted in position 17 beta, not substituted in position 17 alfa
- C07J1/0022—Androstane derivatives substituted in position 17 beta, not substituted in position 17 alfa the substituent being an OH group free esterified or etherified
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Steroid Compounds (AREA)
Description
Verfahren zur Darstellung eines ungesättigten Alkohols. Im Hauptpatent Nr. 184420 sowie seinen Zusatzpatenten ist ein Verfahren zur Dar stellung gesättigter Alkohole vom Typus des Androstandiols durch Reduktion der zu Grunde liegenden Oxyketone bezw. ihrer Derivate in saurer, neutraler oder alkalischer Lösung beschrieben.
Es wurde nun gefunden, dass man in ähnlicher Weise zu entsprechenden ungesät tigten Alkoholen bezw. ihren Derivaten ge langen kann, wenn man Verbindungen vom Typus des Dehydroandrosterons bezw. ihre an der Hydroxylgruppe substituierten Deri vate in neutraler bezw. alkalischer Lösung reduziert.
Als Reduktionsmittel kommen Al kalimetalle in Gegenwart von Alkoholen, Aluminiumalkoholate (Alumiriium-isopropylat oder -benzylat), Organometallverbindungen wie Magnesiumalkylhalogenide oder kataly tisch angeregter Wasserstoff in Betracht. Im letzteren Falle verwendet man zweckmässig unedle oder edle Metallkatalysatoren wie z. B. Nickel, Kobalt oder Platinoxyd und als Lösungsmittel insbesondere niedere aliphati-- sche Alkohole.
Überraschenderweise wird nach vorliegen dem Verfahren die Kohlenstoffdoppelbindung nicht angegriffen, sondern lediglich die vor handene Ketogruppe zur G arbinolgruppe re duziert.
So gelangt man z. B. ausgehend von d5,"-trans-Dehydroandroster-on [d'"-3-Oxy- ätio-cholenon-(17)] der Formel I zum d5,6- trans-Androstendiol-(3,17) der Formel II:
EMI0001.0029
Anstatt von den freien Oxyketonen kann man auch von ihren Derivaten z. B. ihren Estern oder Äthern ausgehen.
Gegenstand des vorliegenden Patentes bildet ein Verfahren zur Darstellung eines ungesättigten Alkohols, welches dadurch ge kennzeichnet ist, dass man auf d5,s-trans-De- hydroandrosteron Wasserstoff in Gegenwart von Metallkatalysatoren in einem neutralen organischen Lösungsmittel einwirken lässt.
Das so gewonnene d5,1-Androeten-3,17- diol bildet Kristalle vorn F. 183,5-184,50. Die neue Verbindung soll therapeutische Verwendung finden oder als Zwischenprodukt zur Herstellung therapeutisch wirksamer Ver bindungen dienen.
Beispiel <I>1:</I> 2 Teile d5,6-trans-Dehydroandrosteron werden in 150 Teilen Alkohol gelöst und unter Zusatz von 7,5 Teilen eines träger- haltigen Nickelkatalysators mit Wasserstoff unter einem Überdruck von 2'/2 Meter Wasser säule geschüttelt. Nach wenigen Stunden ist die für 1 Mol berechnete Menge Wasserstoff aufgenommen. Der Katalysator wird abfiltriert und der Alkohol zum grössten Teil verdampft. Aus dem Rückstand kristallisiert reines ,4',l-Androsten-3,17-diol vom F.183,5-184,5 aus.
Aus der Mutterlauge können noch wei tere Mengen des Diols gewonnen werden. <I>Beispiel 2:</I> <B>100</B> Teile Platinoxyd werden in absolutem Alkohol durch Schütteln mit Wasserstoff vorreduziert. Nach Zusatz von 174 Teilen trans-Debydroandrosteron wird weiter ge schüttelt bis 1 Mol Wasserstoff aufgenommen ist. Nach dem Aufarbeiten erhält man das ungesättigte Diol vom F. 183,5-184,50.
Process for the preparation of an unsaturated alcohol. In the main patent no. 184420 and its additional patents is a process for the Dar position of saturated alcohols of the androstandiol type by reducing the underlying oxyketones BEZW. their derivatives are described in acidic, neutral or alkaline solution.
It has now been found that in a similar manner to corresponding unsaturated alcohols BEZW. their derivatives can ge long when compounds of the dehydroandrosterone type BEZW. their derivatives substituted on the hydroxyl group in neutral respectively. alkaline solution.
As reducing agents, alkali metals in the presence of alcohols, aluminum alcoholates (aluminum isopropylate or benzylate), organometallic compounds such as magnesium alkyl halides or catalyzed hydrogen are suitable. In the latter case, it is useful to use base or noble metal catalysts such as. B. nickel, cobalt or platinum oxide and, as solvents, in particular lower aliphatic alcohols.
Surprisingly, according to the present process, the carbon double bond is not attacked, but only the keto group present is reduced to the garbinol group.
So you get z. B. starting from d5, "- trans-Dehydroandroster-one [d '" - 3-Oxy- ätio-cholenon- (17)] of the formula I to the d5,6-trans-androstenediol- (3,17) of the formula II :
EMI0001.0029
Instead of the free oxyketones one can also use their derivatives z. B. run out of their esters or ethers.
The subject of the present patent is a process for the preparation of an unsaturated alcohol, which is characterized in that hydrogen is allowed to act on d5, s-trans-dehydroandrosterone in the presence of metal catalysts in a neutral organic solvent.
The d5,1-androeten-3,17-diol obtained in this way forms crystals from F. 183.5-184.50. The new compound should find therapeutic use or serve as an intermediate for the preparation of therapeutically effective compounds.
Example <I> 1 </I> 2 parts of d5,6-trans-dehydroandrosterone are dissolved in 150 parts of alcohol and, with the addition of 7.5 parts of a supported nickel catalyst, water is added with hydrogen under a pressure of 2½ meters column shaken. After a few hours, the amount of hydrogen calculated for 1 mole has been absorbed. The catalyst is filtered off and most of the alcohol is evaporated. Pure 4 ', l-androstene-3,17-diol, melting at 183.5-184.5, crystallizes out of the residue.
Further amounts of the diol can be obtained from the mother liquor. <I> Example 2: </I> <B> 100 </B> parts of platinum oxide are prereduced in absolute alcohol by shaking with hydrogen. After adding 174 parts of trans-debydroandrosterone, shaking is continued until 1 mol of hydrogen is absorbed. After working up, the unsaturated diol has a melting point of 183.5-184.50.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH184420T | 1934-10-31 | ||
| CH192062T | 1935-09-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH192062A true CH192062A (en) | 1937-07-15 |
Family
ID=25721026
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH192062D CH192062A (en) | 1934-10-31 | 1935-09-04 | Process for the preparation of an unsaturated alcohol. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH192062A (en) |
-
1935
- 1935-09-04 CH CH192062D patent/CH192062A/en unknown
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