DE673486C - Process for the racemization of optically active ephedrine and pseudo-ephedrine - Google Patents
Process for the racemization of optically active ephedrine and pseudo-ephedrineInfo
- Publication number
- DE673486C DE673486C DEB177353D DEB0177353D DE673486C DE 673486 C DE673486 C DE 673486C DE B177353 D DEB177353 D DE B177353D DE B0177353 D DEB0177353 D DE B0177353D DE 673486 C DE673486 C DE 673486C
- Authority
- DE
- Germany
- Prior art keywords
- ephedrine
- optically active
- racemization
- pseudo
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C215/22—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being unsaturated
- C07C215/28—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being unsaturated and containing six-membered aromatic rings
- C07C215/30—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being unsaturated and containing six-membered aromatic rings containing hydroxy groups and carbon atoms of six-membered aromatic rings bound to the same carbon atom of the carbon skeleton
Description
Verfahren zur Racemisierung von optisch aktivem Ephedrin und Pseudo-Ephedrin Es ist schon oft versucht worden, optisch aktives Ephedrin zu racemisieren. So versuchte Schmidt (Archiv der Pharmazie, Bd.244, S.239-240) 1-Ephedrin durch Erhitzen mit der zehnfachen Menge Salzsäure zu inaktivieren. Dabei wurde jedoch d-ps-Ephedrinerhalten. E m d e 'bestätigte diesen Befund (Archiv ,a. a. O., S.24¢). Im Archiv a. a. O., Bd. 250, S. 154 ff. beschreibt S c h m i d t weitere Racemisierungsversuche. Nach diesen Versuchen konnte durch Einwirkung von Baryt bei Temperaturen von 2 i o° außer Zersetzung keine Inaktivierung beobachtet werden. d-ps-Ephedrin ergab bei Einwirkung von Baryt Bariumhydroxydlösung 1-Ephedrin.Process for the Racemization of Optically Active Ephedrine and Pseudo-Ephedrine Attempts have often been made to racemize optically active ephedrine. Schmidt (Archiv der Pharmazie, Vol. 244, pp. 239-240) tried to inactivate 1-ephedrine by heating it with ten times the amount of hydrochloric acid. However, d-ps-ephedrine was obtained. E mde 'confirmed this finding (archive, op. Cit., P.24 ¢). In the archive loc. Cit., Vol. 250, p. 154 ff., Schmidt describes further attempts at racemization. According to these tests, no inactivation other than decomposition could be observed due to the action of barite at temperatures of 20 °. When exposed to barite, d-ps-ephedrine gave barium hydroxide solution 1-ephedrine.
1-Ephedrin wird auch durch alkoholische Kalilauge nicht verändert und durch Schwefelsäure in d-ps-Ephedrin übergeführt. 1-Ephedrin und d-ps-Ephedrin hergaben bei der B:eha.ndlung mit Essigsäureanhydrid d-ps-Aoetylephedrin. Mit salpetriger Säure erhält man 1-Ephedrin d-ps-Ephedrin. Bei keinem der Versuche konnte Inaktivierung beobachtet werden. Auch S p ä t h (Berichte der deutschen chemischen Gesellschaft, Bd. 58, S. i9'7 und 1268) gelang es nicht, optisch aktives Ephedrin oder ,ps-Ephedrin zu racemiseren.1-ephedrine is not changed by alcoholic potassium hydroxide solution either and converted to d-ps-ephedrine by sulfuric acid. 1-ephedrine and d-ps-ephedrine given by the B: treatment with acetic anhydride d-ps-aoetylephedrine. With nitrous Acid gives 1-ephedrine d-ps-ephedrine. Inactivation failed in any of the attempts to be observed. Also S p ä t h (reports of the German chemical society, Vol. 58, pp. 19'7 and 1268) it was not possible to obtain optically active ephedrine or, ps-ephedrine to racemize.
Es zeigte sich nun überraschenderweise, daß schop geringe Mengen Alkalialkoholat eine vollständige Racemislerung von optisch aktivem Ephedrin und Pseudo-Ephedrin bewirken, und zwar werden als Racem.verbindungen d-1-Ephedrin und d-1-Ps-eudo-Ephedrin erhalten.It has now been found, surprisingly, that even small amounts of alkali metal alcoholate a complete racemization of optically active ephedrine and pseudo-ephedrine cause, namely as Racem.verbindungen d-1-ephedrine and d-1-Ps-eudo-ephedrine obtain.
Die Racemisierung kann sowohl im Schmelzfluß als auch in Lösung bei höheren Temperaturen ausgeführt werden. Als Lösungsmittel kommen hochsiedende, indifferente Kohlenwasserstoffe, ferner Alkohole, wie Benzylalkohol, in Frage. Beispiele i. i g Natrium wird in 2o ccm Methanol gelöst und die Lösung mit 5oo ccm Dekahydronaphthalin und 6o g 1-Ephedrin versetzt. Anschließend destilliert man i 2o ccm bei gewöhnlichem Druck ab und erhitzt den Kolbeninhalt 4 Stunden zum Sieden, wobei die Innentemperatur etwa 195' ist. Dann wird abgekühlt und werden die Basen mit verdünnter Schwefelsäure aus der D:ekahydronaphthaJinlösung ausgeschüttelt. Die schwefelsaure Lösung wird stark alkalisch gemacht, und die ausfallenden Basen werden mit Äther aufgenommen. Der Ätherrückstand wird mit Salzsäure neutral gelöst -und mit- Kaliumoxalatlösung versetzt. Das .auskristallisierende Oxalat ist d-1-Ephedrinoxalat. Aus der Mutterlauge fällt mit Kalilauge dl-ps-Ephedrin,. Ausbeute 53% dl-ps-Ephedrin und ¢20,'o dl-Ephedrin.The racemization can take place both in the melt flow and in solution run at higher temperatures. High-boiling, indifferent solvents are used as solvents Hydrocarbons, and also alcohols such as benzyl alcohol, are possible. Examples i. i g of sodium is dissolved in 20 cc of methanol and the solution with 500 cc of decahydronaphthalene and 60 g of 1-ephedrine were added. Then i 2o cc is distilled in the usual way Pressure and heats the contents of the flask to the boil for 4 hours, the Internal temperature is about 195 '. Then it is cooled and the bases are diluted with sulfuric acid Shaken out of the d: ekahydronaphthaJin solution. The sulfuric acid solution will made strongly alkaline, and the precipitating bases are taken up with ether. The ether residue is dissolved neutrally with hydrochloric acid and with potassium oxalate solution offset. The .crystallizing oxalate is d-1-ephedrine oxalate. From the mother liquor falls with potassium hydroxide dl-ps-ephedrine ,. Yield 53% of dl-ps-ephedrine and [20, 'o dl-ephedrine.
2. 2 g Natrium werden in 4o ccm Methanol gelöst und mit 3o g d-ps-Epliedrin und 30o ccm D,ekahydronaphthalin versetzt. Anschließend werden i2occm des Lösungsmittels abdestilliert, und der Kolbenrückstand wird 2 Stunden zum Sieden erhitzt. Die Weiterverarbeitung erfolgt wie in Beispiel i.2. 2 g of sodium are dissolved in 40 cc of methanol and mixed with 3o g of d-ps-Epliedrin and 30o cc D, ekahydronaphthalene added. Then i2occm of the solvent distilled off, and the flask residue is heated to boiling for 2 hours. The further processing takes place as in example i.
Ausbeute : 50,7 % dl - ps - Ephedrin und 42,7 0,'o dl-Eph,-drin.Yield: 50.7% dl-ps-ephedrine and 42.7% dl-eph-drin.
3. i g Natrium wird in 20 ccm Aalethanol gelöst und die Lösung mit 30 g 1-Ephedrin versetzt. Dann wird das Methanol abdestilliert. Die entstandene klare Schmelze wird 2 Stunden auf i 9o' -erhitzt, darauf mit verdünnter Salzsäure neutralisiert und wie im Beispiel i mit Kaliumoxalatlösung versetzt und aufgearbeitet. Ausbeute 49% dl-ps-Ephedrin und 45% dl-Ephedrin.3. ig sodium is dissolved in 20 cc of eel ethanol and 30 g of 1-ephedrine are added to the solution. Then the methanol is distilled off. The resulting clear melt is heated to 150 'for 2 hours, then neutralized with dilute hydrochloric acid and, as in Example 1, mixed with potassium oxalate solution and worked up. Yield 49% dl-ps-ephedrine and 45% dl-ephedrine.
4.. 409 metallisches Natrium werden in ,i Soo ccm Amylalkohol gelöst. Anschließend werden iooo ccm Amylalkohol abdestilliert. Zur konzentrierten Natriumamylatlösung werden nun Sog 1-Eph.edrinbase hinzugegeben und das Ganze 42 Stunden gekocht. Nach dem Abkühlen werden die entstandenen Basen mif Schwefelsäure ausgeschüttelt. Aus der schwefelsauren Lösung werden die Basen durch Fällen mit Natronlauge und Ausschütteln mit Äther isoliert und dann in bekannter Weise über das Oxalat getrennt. Ausbeute: 59 g d-l-E.phedrinoxalat, 15 g -d-1-ps-Ephedrinbase.4 .. 409 metallic sodium are dissolved in 1.500 cc of amyl alcohol. Then 100 ccm of amyl alcohol are distilled off. Sog 1-Eph.edrine base is now added to the concentrated sodium amylate solution and the whole thing is boiled for 42 hours. After cooling, the resulting bases are shaken out with sulfuric acid. The bases are isolated from the sulfuric acid solution by precipitation with sodium hydroxide solution and shaking out with ether and then separated in a known manner via the oxalate. Yield: 59 g dlE.phedrine oxalate, 15 g -d-1-ps-ephedrine base.
Claims (1)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEB177353D DE673486C (en) | 1937-02-13 | 1937-02-13 | Process for the racemization of optically active ephedrine and pseudo-ephedrine |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEB177353D DE673486C (en) | 1937-02-13 | 1937-02-13 | Process for the racemization of optically active ephedrine and pseudo-ephedrine |
Publications (1)
Publication Number | Publication Date |
---|---|
DE673486C true DE673486C (en) | 1939-03-24 |
Family
ID=7008167
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DEB177353D Expired DE673486C (en) | 1937-02-13 | 1937-02-13 | Process for the racemization of optically active ephedrine and pseudo-ephedrine |
Country Status (1)
Country | Link |
---|---|
DE (1) | DE673486C (en) |
-
1937
- 1937-02-13 DE DEB177353D patent/DE673486C/en not_active Expired
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