CH239877A - Process for the preparation of 3,17-dioxy-etiocholen-aldehyde. - Google Patents
Process for the preparation of 3,17-dioxy-etiocholen-aldehyde.Info
- Publication number
- CH239877A CH239877A CH239877DA CH239877A CH 239877 A CH239877 A CH 239877A CH 239877D A CH239877D A CH 239877DA CH 239877 A CH239877 A CH 239877A
- Authority
- CH
- Switzerland
- Prior art keywords
- double bond
- dioxy
- aldehyde
- androstens
- ether
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 11
- 238000002360 preparation method Methods 0.000 title description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 3
- 239000012433 hydrogen halide Substances 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- DLLJVQNYBYOKGS-UHFFFAOYSA-N ethoxyethane;pentane Chemical compound CCCCC.CCOCC DLLJVQNYBYOKGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- -1 styryl androstene Chemical compound 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- MJOQJPYNENPSSS-XQHKEYJVSA-N [(3r,4s,5r,6s)-4,5,6-triacetyloxyoxan-3-yl] acetate Chemical compound CC(=O)O[C@@H]1CO[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O MJOQJPYNENPSSS-XQHKEYJVSA-N 0.000 description 1
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 description 1
- SLUNEGLMXGHOLY-UHFFFAOYSA-N benzene;hexane Chemical compound CCCCCC.C1=CC=CC=C1 SLUNEGLMXGHOLY-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 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
- 239000012259 ether extract Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002044 hexane fraction Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229960001566 methyltestosterone Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 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
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229960002847 prasterone Drugs 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 150000007659 semicarbazones Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J3/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, substituted in position 17 beta by one carbon atom
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 von 3,17-Dio$y-ätioeholen-aldehyd. Gegenstand des vorliegenden Patentes ist ein Verfahren zur Herstellung von 3,17- Dioxy-äthiocholen-aldehyd, das dadurch ge kennzeichnet ist, dass man ein Derivat des A '-3,17-Dioxy-androstens, welches in 17- Stellung eine Seitenkette mit einer zum C Atom 17 benachbarten Doppelbindung auf weist, und bei welchem im Vergleich zum zf'-3@,17-Dioxy-androsten mindestens eine der Hydroxylgruppen durch einen Rest substi tuiert ist,
welcher durch Hydrolyse im End produkt die freie 0$-Gruppe ergibt, unter intermediärem Schutz der Kerndoppelbin- dung, mit einem Mittel behandelt, welches die Doppelbindung in der Seitenkette oxy- dativ aufspaltet, den so erhaltenen Aldehyd isoliert und durch Hydrolyse die GH-Grup- pen herstellt.
Die Verbindung dient als Ausgangspro dukt für die Herstellung des Corpuslutcum- Hormons. Si-, schmilzt aus Äther-Pentan um kristallisiert bei 137-139 C. Als Ausgangsstoffe eignen sich insbeson dere die 3,17-Ester bezw. -Äther des d'-3,17 Dioxy-17-vinyl- bezw. -styryl-androstens.
Zum intermediären Schutz der Ring doppelbindung bedient man sich vorteilhaft der Anlagerung von Halogenwasserstoff oder Halogen, insbesondere Brom. Die Doppelbin dung der Seitenkette wird hierbei nicht an gegriffen.
Die Wiederherstellung der Doppelbindung nach erfolgter Oxydation kann in bekannter Weise, zum Beispiel durch Behandlung der Dihalogenide mit Zinkstaub in Eisessiglö- sung, oder im Falle der Halogenwasserstoff anlagerung, mit Pyridin und andern bekann ten Mitteln, wie sie zum Beispiel in Houben- Weyl "Die Methoden der organischen Chemie" Bd. 3, 2. Auflage (1923), S. 209fF. bezw. Bd. 2, 2.
Auflage (1922), S.'744-ff. beschrie ben sind, geschehen.
Als Oxydationsmittel verwendet man mit Vorteil Ozon, Chromsäure, Tetraacetate des Bleis oder Mangans, Permanganate usw. <I>Beispiel 1:</I> 2 g d '-3,17-Diacetoxy-17-vinyl-androsten -erden in 200 ein' Tetrachlorkohlenstoff ge löst und mit. 0,5 ein' Pyridin versetzt.
Hierzu gibt man unter Rühren<B>0,799</B> g Brom (1 Mol) in 50 cm' Tetrachlorkohlenstoff. Nach Zu gabe des Broms rührt man noch 1 Stunde weiter und leitet sodann 1 Stunde Ozon durch die Reaktionslösung (Strömungsgeschwindig keit 4 Liter!Stunde bei Verwendung einer Ley denen Flasche). Anschliessend versetzt man mit 200 emd Eisessig und verdrängt das Ozon durch Stickstoff.
Nach ?4 Stunden wird der Tetrachlorkohlenstoff im Vakuum bei 30 verdampft und zii der Eisessiglösung bei einer Temperatur von zirka 10-20"<B><I>)</I></B> g Zink staub gegeben. Man rührt eine halbe Stunde in der Kälte und die Bleiehe Zeit bei 95-100 . Es wird dann vom Zinkstaub abfiltriert und in Wasser gegossen. Der ausgefallene Nieder sehlax wird in Benzol aufgenommen und das Benzol mit Wasser gewaschen, uni den Eis essig zu entfernen.
Die bei der Ozonisierung entstandenen Säuren werden mit Alkali aus der Benzol- lösung ausgeschüttelt.
Die von den Säuren befreite Benzollösung wird mit Wasser neutral gewaschen und ver dampft. Den Rückstand erwärmt man gelinde mit einer Lösung von Seinicai#bacidaeetiit in lIetlianol, wobei sich ein Niederschlag nicht ausscheidet. Man nimmt in viel Äther auf und wäscht den Äther mit. Alkali und Wasser.
Den nach Eindampfen des Äthers erhaltenen Rückstand verreibt man mit wenig Äther und saugt das auf diese Weise gereinigte Semi- carbazon des 3,17-Diacetoxy-ätiocholen-aIde- hy ds ab, aus dem man nach .Spaltung mit Benzaldehyd und Hydrolyse den freien 3,17- Dioxy-ätiocholen-aldeliyd gewinnt.
<I>Beispiel 2:</I> 1 g Dehydroandrosteron-acetat wird in 100 cm3 abs. Äther mit 8 g Bromstyrol und dann mit einigen Stücken aktiviertem Li- thiummetall versetzt. Man unterbricht die lebhafte Reaktion sobald sich eine beständige braunrote Farbe eingestellt hat. zersetzt mit Alkohol und Wasser, äthert aus und behan delt den eingedampften Extrakt im Vakuum mit Wasserdampf so lange, bis die letzten Reste von Bromstvrol verschwunden sind.
Man nimmt in Benzol auf, trocknet, versetzt reit. dem halben Volumen Hexan und chro- matographiert über 25 g Aluminiumoxyd.
Die Benzol-Hexanfraktion wird verworfen und das Aluminiumoxyd mit Benzol/Alkohol (50:1) eluiert; das Eluat hinterlässt beim Eindampfen das 3-11onoacetoxy-17-oxy-17- sty ryl-androsten als klares Bartes Glas (Iso- in erengeniisch) .
e Zur Bereitung des 3-Monoacetoxy-17-oxy- ätiocholei-aldeliyds wird in reinstem Essig ester (20 ein') gelöst, mit 1 1flol Brom (-= 484 nix, gelöst in zirka 5 cm' Essigester) versetzt und nach erfolgter Entfärbung e 4 Stunden mit Ozon bei 0 behandelt.
Dann verdrängt man das überschüssige Ozon mit Kohlendioxyd, zerstört das Ozonid mit Zink staub und entbromt anschliessend durch Zu- gabc von weiterem Zinkstaub und etwas Al- s kohol unter Erwärmen. plan filtriert, dampft ab, nimmt in Äther auf, trennt Säuren mit Sololösung ab und kristallisiert den gewa schenen, getrockneten und abgedampften Ätherextrakt ans Aceton.
Ausbeute 300 mg gelbliche Bröckchen; das Präparat gibt deut liche Aldehydreaktion mit fuchsinschwefliger Säure. Es wird, wie im Beispiel 1 angegeben, zum 3,17-Dioxy-ätiocholen-5-aldehyd aufge arbeitet. F
Process for the preparation of 3,17-Dio $ y-etioeholen-aldehyde. The subject of the present patent is a process for the preparation of 3,17-dioxy-ethiocholen-aldehyde, which is characterized in that a derivative of A '-3,17-dioxy-androstens, which has a side chain in the 17-position has a double bond adjacent to the carbon atom 17, and in which at least one of the hydroxyl groups is substituted by a radical compared to zf'-3 @, 17-dioxy-androstene,
which gives the free 0 $ group by hydrolysis in the end product, with intermediate protection of the core double bond, treated with an agent which oxidatively splits the double bond in the side chain, isolates the aldehyde obtained and hydrolyses the GH group - manufactures pen.
The compound serves as a starting product for the manufacture of the corpuslutcum hormone. Si, melts from ether-pentane to crystallize at 137-139 C. As starting materials are in particular the 3,17 esters respectively. -Ather des d'-3,17 Dioxy-17-vinyl- respectively. -styryl-androstens.
For the intermediate protection of the ring double bond, it is advantageous to use the addition of hydrogen halide or halogen, in particular bromine. The double binding of the side chain is not affected.
The double bond can be restored in a known manner, for example by treating the dihalides with zinc dust in glacial acetic acid solution, or, in the case of hydrogen halide addition, with pyridine and other known agents, such as those described in Houben-Weyl "Die Methods of organic chemistry "Vol. 3, 2nd edition (1923), pp. 209fF. respectively Vol. 2, 2.
Edition (1922), pp. 744-ff. have been described.
The oxidizing agent used is advantageously ozone, chromic acid, tetraacetate of lead or manganese, permanganate, etc. <I> Example 1: </I> 2 gd '-3,17-diacetoxy-17-vinyl-androstene in 200 a' Carbon tetrachloride dissolved and with. 0.5 a pyridine added.
To this end, 0.799 g of bromine (1 mol) in 50 cm of carbon tetrachloride are added with stirring. After adding the bromine, stirring is continued for 1 hour and then ozone is passed through the reaction solution for 1 hour (flow rate 4 liters! Hour when using a Ley those bottle). Then 200 emd glacial acetic acid is added and the ozone is displaced by nitrogen.
After 4 hours, the carbon tetrachloride is evaporated in vacuo at 30 and added to the glacial acetic acid solution at a temperature of about 10-20 g zinc dust. The mixture is stirred for half an hour in the cold and the lead time at 95-100. The zinc dust is then filtered off and poured into water. The precipitated low-sehlax is taken up in benzene, and the benzene is washed with water to remove the glacial vinegar.
The acids produced during ozonization are shaken out of the benzene solution with alkali.
The benzene solution freed from the acids is washed neutral with water and evaporated. The residue is warmed gently with a solution of Seinicai # bacidaeetiit in lietlianol, a precipitate not separating out. One absorbs a lot of ether and washes the ether with it. Alkali and water.
The residue obtained after evaporation of the ether is triturated with a little ether and the thus purified semi-carbazone of 3,17-diacetoxy-ethiocholen-aldehyde is sucked off, from which, after cleavage with benzaldehyde and hydrolysis, the free 3 , 17-Dioxy-etiocholen-aldeliyd wins.
<I> Example 2: </I> 1 g of dehydroandrosterone acetate is dissolved in 100 cm3 of abs. Ether with 8 g of bromostyrene and then mixed with a few pieces of activated lithium metal. The lively reaction is interrupted as soon as a steady brown-red color has established itself. decomposes with alcohol and water, etherifies and treats the evaporated extract in vacuo with steam until the last remains of bromostvrol have disappeared.
You take up in benzene, dry, and ride. half the volume of hexane and chromatographed over 25 g of aluminum oxide.
The benzene-hexane fraction is discarded and the aluminum oxide is eluted with benzene / alcohol (50: 1); the eluate leaves the 3-11onoacetoxy-17-oxy-17-styryl-androsten as a clear Bartes glass (iso-in-erengeniisch).
e To prepare the 3-monoacetoxy-17-oxy-ätiocholei-aldeliyds, it is dissolved in the purest ethyl acetate (20%), mixed with 1 liter of bromine (- = 484 nothing, dissolved in about 5 cm 'of ethyl acetate) and after the color has been removed e treated with ozone at 0 for 4 hours.
Then the excess ozone is displaced with carbon dioxide, the ozonide is destroyed with zinc dust and then brominated by adding more zinc dust and some alcohol while warming. Filtered flat, evaporated, absorbed in ether, separated acids with a solution and crystallized the washed, dried and evaporated ether extract on acetone.
Yield 300 mg of yellowish lumps; the preparation gives clear aldehyde reaction with fuchsin-sulphurous acid. As indicated in Example 1, it is worked up to 3,17-dioxy-etiocholen-5-aldehyde. F.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE239877X | 1937-06-21 | ||
| CH217761T | 1938-06-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH239877A true CH239877A (en) | 1945-11-15 |
Family
ID=25726054
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH239877D CH239877A (en) | 1937-06-21 | 1938-06-09 | Process for the preparation of 3,17-dioxy-etiocholen-aldehyde. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH239877A (en) |
-
1938
- 1938-06-09 CH CH239877D patent/CH239877A/en unknown
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