CH189064A - Process for the preparation of a stereoisomeric alcohol. - Google Patents
Process for the preparation of a stereoisomeric alcohol.Info
- Publication number
- CH189064A CH189064A CH189064DA CH189064A CH 189064 A CH189064 A CH 189064A CH 189064D A CH189064D A CH 189064DA CH 189064 A CH189064 A CH 189064A
- Authority
- CH
- Switzerland
- Prior art keywords
- process according
- catalysts
- works
- reduction
- carried out
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 6
- 150000002009 diols Chemical class 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- QGXBDMJGAMFCBF-LUJOEAJASA-N epiandrosterone Chemical compound C1[C@@H](O)CC[C@]2(C)[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CC[C@H]21 QGXBDMJGAMFCBF-LUJOEAJASA-N 0.000 claims description 2
- 230000001766 physiological effect Effects 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 2
- 239000010953 base metal Substances 0.000 claims 1
- 230000001225 therapeutic effect Effects 0.000 claims 1
- 235000019441 ethanol Nutrition 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical class O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 2
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229930182558 Sterol Natural products 0.000 description 1
- 239000003613 bile acid Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910017052 cobalt 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
- 150000002148 esters Chemical class 0.000 description 1
- 150000002431 hydrogen 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003432 sterols Chemical class 0.000 description 1
- 235000003702 sterols Nutrition 0.000 description 1
- 238000002560 therapeutic procedure Methods 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 Herstellung eines stereolsomeren Alkohols. Im Patent Nr. 182391 ist die Herstellung mehrkerniger Ringketone aus Sterinen und Gallensäuren beschrieben. Es wurde nun ge funden, dass man durch Hydrierung solcher Ringketone jeweils zwei stereoisomere Alko hole erhalten kann.
Dabei ist man durch passende Wahl der Reaktionsbedingungen, insbesondere durch saure oder neutrale bezw. alkalische Einstellung des Mediums, in dem reduziert wird, oft in der Lage, vorzugsweise oder ausschliesslich den einen oder andern der jeweils möglichen beiden stereoisomeren Alkohole zu gewinnen.
Letztere leiten sich von den zugrunde liegenden Ketonen derart -il), da.ss die bei der Hydrierung der Keton- gruppe entstehende Hydroxylgruppe im einen Falle auf der einen Seite des Ring systems und im andern Falle auf seiner ent gegengesetzten Seite steht.
Als Ausgangsprodukte können sowohl die nach dem in obiger Patentschrift ange gebenen Verfahren hergestellten Oxyketone, wie auch ihre Derivate z. B. ihre Ester, Äther oder dergleichen: dienen. Die Verwen dung von Oxyketonen führt zu stereoisome- ren Diolen. Die Reduktion wird zweckmässig mit aktiviertem Wasserstoff ausgeführt, so z.
B. durch Hydrierung mit Wasserstoff in Gegenwart von Katalysatoren der Platin gruppe, von Nickel, Kobalt, von Kataly- satorgemischen und dergleichen., oder auch mit naszierendem Wasserstoff, z. B. Natrium in Alkoholen:. Als Lösungsmittel für die katalytische Hydrierung lassen sich Eis- essig, Alkohole, wie Methyl- oder Äthyl- alkohol, Äther, usw. verwenden.
Gegenstand des vorliegenden Patentes bildet ein Verfahren zur Herstellung eines stereoisomeren Alkohols, welches dadurch gekennzeichnet ist, dass man trans-Androste- ron mit Reduktionsmitteln behandelt und das entstandene trans-Androstandiol vom F.<B>168'</B> (korr.) isoliert. Das so gewonnene Diol kann aus Essigester umkristallisiert werden.
Es zeichnet sich durch .seine phisio- iobisehe Wirkung aus und soll therapeu tische Verwendung finden.
Beispiel: \?90 m.; trans-Androsteron werden in 6 cm-' Eisessig mit Platinoxyd (34 mb) und Urasser-4off reduziert. Die Wasserstoffauf nahme beträgt 1 Mol und ist nach kurzer Zeit beendet.
Man filtriert vom Iiatrflysator ab, ver dünnt mit Wasser und nimmt das Reduk- tionsprodukt in Äther auf. Die neutral ge waschene Ätherlösung wird eingedampft und der Rückstand aus Essigester um kristallisiert. Man erhält sofort ein einheit liches Diol, das gut getrocknet bei l:68 (korr.) schmilzt.
Process for the preparation of a stereolomeric alcohol. Patent No. 182391 describes the production of polynuclear ring ketones from sterols and bile acids. It has now been found that by hydrogenating such ring ketones, two stereoisomeric alcohols can be obtained.
One is through a suitable choice of the reaction conditions, in particular through acidic or neutral respectively. alkaline setting of the medium in which the reduction is carried out, often able to obtain preferably or exclusively one or the other of the two possible stereoisomeric alcohols.
The latter are derived from the underlying ketones in such a way that the hydroxyl group formed during the hydrogenation of the ketone group is on one side of the ring system in one case and on its opposite side in the other.
As starting products, both the oxyketones prepared according to the method given in the above patent, as well as their derivatives, for. B. their esters, ethers or the like: serve. The use of oxyketones leads to stereoisomeric diols. The reduction is conveniently carried out with activated hydrogen, e.g.
B. by hydrogenation with hydrogen in the presence of catalysts of the platinum group, of nickel, cobalt, of catalyst mixtures and the like., Or with nascent hydrogen, z. B. Sodium in Alcohols: Glacial acetic acid, alcohols such as methyl or ethyl alcohol, ethers, etc. can be used as solvents for the catalytic hydrogenation.
The subject of the present patent is a process for the preparation of a stereoisomeric alcohol, which is characterized in that trans-androste- rone is treated with reducing agents and the resulting trans-androstandiol from F. 168 '(corr.) isolated. The diol obtained in this way can be recrystallized from ethyl acetate.
It is characterized by its physiological effect and is intended to be used in therapy.
Example: \? 90 m .; trans-Androsteron are reduced in 6 cm- 'glacial acetic acid with platinum oxide (34 mb) and urasser-4off. The hydrogen uptake is 1 mol and is over after a short time.
It is filtered off from the Iiatrflysator, diluted with water and the reduction product is taken up in ether. The ether solution washed neutrally is evaporated and the residue is crystallized from ethyl acetate. A uniform diol is obtained immediately which, when dry, melts at 1:68 (corr.).
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH184420T | 1934-10-31 | ||
| CH189064T | 1934-10-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH189064A true CH189064A (en) | 1937-01-31 |
Family
ID=25721024
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH189064D CH189064A (en) | 1934-10-31 | 1934-10-31 | Process for the preparation of a stereoisomeric alcohol. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH189064A (en) |
-
1934
- 1934-10-31 CH CH189064D patent/CH189064A/en unknown
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