CH314796A - Process for the production of 7-dehydro-cholesterol - Google Patents
Process for the production of 7-dehydro-cholesterolInfo
- Publication number
- CH314796A CH314796A CH314796DA CH314796A CH 314796 A CH314796 A CH 314796A CH 314796D A CH314796D A CH 314796DA CH 314796 A CH314796 A CH 314796A
- Authority
- CH
- Switzerland
- Prior art keywords
- dehydro
- cholesterol
- ester
- production
- bromo
- Prior art date
Links
- UCTLRSWJYQTBFZ-UHFFFAOYSA-N Dehydrocholesterol Natural products C1C(O)CCC2(C)C(CCC3(C(C(C)CCCC(C)C)CCC33)C)C3=CC=C21 UCTLRSWJYQTBFZ-UHFFFAOYSA-N 0.000 title claims description 8
- 238000000034 method Methods 0.000 title claims description 8
- QYSXJUFSXHHAJI-YRZJJWOYSA-N vitamin D3 Chemical compound C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)CCCC(C)C)=C\C=C1\C[C@@H](O)CCC1=C QYSXJUFSXHHAJI-YRZJJWOYSA-N 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 14
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- 230000001419 dependent effect Effects 0.000 claims 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000011541 reaction mixture Substances 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 239000000243 solution Substances 0.000 description 6
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- IHOQNBAZWVTKFK-BVBBTSNESA-N cholesta-5,7-dien-3beta-ol benzoate Chemical compound O([C@@H]1CC2=CC=C3[C@@H]4CC[C@@H]([C@]4(CC[C@@H]3[C@@]2(C)CC1)C)[C@H](C)CCCC(C)C)C(=O)C1=CC=CC=C1 IHOQNBAZWVTKFK-BVBBTSNESA-N 0.000 description 1
- 235000012000 cholesterol Nutrition 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J9/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane
-
- 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)
- Steroid Compounds (AREA)
Description
Verfahren zur Herstellung von 7.Dehydro.cholesterin Es ist bekannt, dass man 7-Dehydro-chole- sterin aus 7-Brom-cholesterylestern herstellen kann, indem man auf die siedende Lösung eines 7-Brom-eholesterylesters in einem iner- ten Lösungsmittel konzentrierte wässerige Lö sungen von Alkalihydroxyden oder Alkali- carbonaten einwirken lässt.
Gegenstand des vorliegenden Patentes ist ein Verfahren zur Herstellung von 7-Dehydro- eholesterin durch Bromwasserstoffabspaltung aus einem 7-Brom-cholesterylester und an schliessende Verseifung des gebildeten 7-De- hy dro-cholesterylesters, das dadurch gekenn zeichnet ist, dass man auf eine Lösung des 7-Brom-cholesterylesters in einem inerten was serfreien Lösungsmittel zur Bromwasserstoff- abspaltung gasförmiges Ammoniak einwirken lässt.
Wie sich gezeigt hat, kann man das 7-De- hydro-cholesterin erfindungsgemäss vorteilhaft dadurch erhalten, dass man auf die siedende Lösung eines 7-Brom-cholesterylesters in einem inerten wasserfreien Lösungsmittel gasförmi ges Ammoniak so lange einwirken lässt, bis allegBrom als Bromwasserstoff abgespalten ist und die fast farblose Lösung des gebilde ten 7-Dehydro-cholesterinesters anschliessend durch Verseifung in das freie 7-Dehydro-cho- lesterin überführt. Man erhält auf diese Weise Produkte, welche fast frei von farbigen Bei mengungen sind.
Diese Arbeitsweise zeichnet sich durch grosse Einfachheit ans, indem durch einfaches Durchleiten von Ammoniak durch die Reaktionslösung sich augenblick lich das HBr als Ammoniumbromid fest abzu scheiden beginnt -und die darüberstehende Lö sung des sich bildenden 7-Dehydro-cholesteryl- esters ohne Beimengungen als solche erhalten bleibt.
<I>Beispiel</I> 20 g 7-Brom-cholesterylbenzoat (oder Ace tat oder ein anderer Ester) werden in einem Rundkolben, versehen mit Gaseinleitungsrohr, Rückflusskühler und Rührer, in 150 cm3 Yylol gelöst und schon in der Kälte ein kräf tiger Ammoniakstrom eingeblasen. Während des Einleitens setzt man den Kolben in ein auf 150 C vorgeheiztes ölbad. Nach 3 bis 4 Minuten beginnt sich das unlösliche Am moniumbromid flockig auszuscheiden.
Nach 3 Stunden ist die Bromwasserstoffabspaltung beendet. Man filtriert von Ammoniumbromid ab und erhält nach der Aufarbeitung und Verseifung 13,0 g eines beinahe weissen Ste- ringemisches, welches 40,50/0. 7-Dehydro-cho- lesterin (spektroskopisch gemessen) enthält.
Die Gesamtausbeute an 7-Dehydro-cholesterin beträgt 46,2%, bezogen auf 100%iges 7-De- hydr o-cholesterylbenzoat.
Process for the preparation of 7.Dehydro.cholesterol It is known that 7-dehydrocholesterol can be prepared from 7-bromo-cholesteryl esters by concentrating on the boiling solution of a 7-bromo-eholesteryl ester in an inert solvent allows aqueous solutions of alkali hydroxides or alkali carbonates to act.
The present patent relates to a process for the production of 7-dehydro-eholesterol by splitting off hydrogen bromide from a 7-bromo-cholesteryl ester and then saponifying the 7-dehydro-cholesteryl ester formed, which is characterized in that it is applied to a solution of the 7-bromo-cholesteryl ester in an inert water-free solvent to split off hydrogen bromide allows gaseous ammonia to act.
As has been shown, the 7-dehydro-cholesterol can advantageously be obtained according to the invention by allowing gaseous ammonia to act on the boiling solution of a 7-bromo-cholesteryl ester in an inert anhydrous solvent until all the bromine is split off as hydrogen bromide and the almost colorless solution of the 7-dehydro-cholesterol ester formed is then converted into the free 7-dehydro-cholesterol by saponification. In this way, products are obtained which are almost free of colored additions.
This procedure is characterized by great simplicity, in that by simply passing ammonia through the reaction solution, the HBr begins to solidly separate out as ammonium bromide - and the overlying solution of the 7-dehydrocholesteryl ester that forms is obtained as such without admixtures remains.
<I> Example </I> 20 g of 7-bromo-cholesteryl benzoate (or acetate or another ester) are dissolved in 150 cm3 of yylene in a round-bottomed flask equipped with a gas inlet tube, reflux condenser and stirrer and a strong drink even in the cold Stream of ammonia blown in. During the introduction, the flask is placed in an oil bath preheated to 150.degree. After 3 to 4 minutes, the insoluble ammonium bromide begins to separate out flaky.
The elimination of hydrogen bromide is complete after 3 hours. Ammonium bromide is filtered off and, after work-up and saponification, 13.0 g of an almost white stone mixture, which is 40.50 / 0. Contains 7-dehydro-cholesterol (measured spectroscopically).
The overall yield of 7-dehydro-cholesterol is 46.2%, based on 100% 7-dehydro-cholesteryl benzoate.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH314796T | 1953-02-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH314796A true CH314796A (en) | 1956-06-30 |
Family
ID=4495739
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH314796D CH314796A (en) | 1953-02-17 | 1953-02-17 | Process for the production of 7-dehydro-cholesterol |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH314796A (en) |
-
1953
- 1953-02-17 CH CH314796D patent/CH314796A/en unknown
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