DE1166783B - Process for the production of DL-proline - Google Patents
Process for the production of DL-prolineInfo
- Publication number
- DE1166783B DE1166783B DEM46764A DEM0046764A DE1166783B DE 1166783 B DE1166783 B DE 1166783B DE M46764 A DEM46764 A DE M46764A DE M0046764 A DEM0046764 A DE M0046764A DE 1166783 B DE1166783 B DE 1166783B
- Authority
- DE
- Germany
- Prior art keywords
- proline
- acid
- production
- keto
- picrate
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D207/10—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/16—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Hydrogenated Pyridines (AREA)
- Pyrrole Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
Verfahren zur Herstellung von DL-Prolin Es wurde gefunden, daß man DL-Prolin erhält, wenn man eine wäßrige, saure Lösung von cc-Ketob-amino-valeriansäure bzw. von der mit ihr im Gleichgewicht stehenden J 1-Pyrrolin-carbonsäure-(2) katalytisch hydriert.Process for the preparation of DL-proline It has been found that one DL-proline is obtained when an aqueous, acidic solution of cc-ketobamino-valeric acid is obtained or from the J 1-pyrroline-carboxylic acid (2) which is in equilibrium with it catalytically hydrogenated.
Es ist dabei nicht notwendig, von isolierter n-Ketob-amino-valeriansäure auszugehen, sondern man kann auch zur Hydrierung unmittelbar eine Lösung von a-Keto-6-amino-valeriansäure bzw. S 1-Pyrrolin-carbonsäure-(2) verwenden, die durch saure Hydrolyse von 2,3 - Dioxo - piperidin - carbonsäure - (4) - äthylester erhalten worden ist. It is not necessary to use isolated n-ketobamino-valeric acid starting, but you can also use a solution of α-keto-6-amino-valeric acid directly for hydrogenation or use S 1-pyrroline-carboxylic acid- (2), which by acid hydrolysis of 2,3 - Dioxo - piperidine - carboxylic acid - (4) - ethyl ester has been obtained.
Beispiel 1 Eine Lösung von ol-Keto-6-amino-valeriansäure, die durch 7 Minuten langes Kochen von 12,5 g 2,3-Dioxo-piperidin-carbonsäure-(4)-äthylester mit 200 ccm 6 n-HCl auf dem Ölbad von 155"C unter Rückfluß und Einengen auf 30 ccm bei 40"C und 25 mm erhalten worden ist, wird mit 120 ccm Wasser verdünnt. Die Hydrierung mit 270 mg PtO2 bei 25"C und 1 Atm. ist nach 5 Stunden beendet. Example 1 A solution of ol-keto-6-amino-valeric acid which is produced by Boiling 12.5 g of 2,3-dioxo-piperidine-carboxylic acid (4) ethyl ester for 7 minutes with 200 cc of 6 N HCl on an oil bath at 155 "C under reflux and concentration to 30 cc at 40 "C and 25 mm is diluted with 120 cc of water. The hydrogenation with 270 mg PtO2 at 25 ° C. and 1 atm. is complete after 5 hours.
Durch Aufgeben auf eine Säule von schwach basischem Anionenaustauscher und Nachspülen mit 1,3 1 Wasser läßt sich die Salzsäure entfernen. Das zur Trockne gebrachte Eluat ergibt aus Äthanol 5,51 g (71 O/o der Theorie) reinen DL-Prolins. Der RF-Wert von 0,54 entspricht dem des käuflichen DL-Prolins. By placing it on a column of weakly basic anion exchanger and rinsing with 1.3 l of water, the hydrochloric acid can be removed. That to dryness The resulting eluate from ethanol gives 5.51 g (71% of theory) of pure DL-proline. The RF value of 0.54 corresponds to that of the commercially available DL-Proline.
Beispiel 2 48,7 mg ou-Keto-b-amino-valeriansäure-hydrochlorid in wenig Wasser werden mit 12g Platinoxyd bei 755 mm und 21"C 3 Stunden in Wasserstoffatmosphäre geschüttelt. Dabei werden 8,1 ccm Wasserstoff aufgenommen. Die Chlorionen werden mit Silberoxyd und Schwefelwasserstoff entfernt, und das Filtrat wird zur Trockne eingedampft. Example 2 48.7 mg of ou-keto-b-amino-valeric acid hydrochloride in a little water with 12 g of platinum oxide at 755 mm and 21 "C for 3 hours in a hydrogen atmosphere shaken. 8.1 ccm of hydrogen are taken up. The chlorine ions will removed with silver oxide and hydrogen sulfide, and the filtrate becomes dry evaporated.
Man nimmt in 950/,dem Alkohol auf, filtriert und dampft zur Trockne. Der Rückstand (26,3 mg) wird mit 48 mg Pikrinsäure in heißem Eisessig gelöst. It is taken up in 950 /, the alcohol, filtered and evaporated to dryness. The residue (26.3 mg) is dissolved with 48 mg of picric acid in hot glacial acetic acid.
Nach Zusatz von Äther fallen 51,1 mg gelbes Pikrat aus. Nach dem Umfällen aus Eisessig/Äther liegt der Schmelzpunkt bei 134 bis 135"C, der Misch-Schmelzpunkt mit DL-Prolin-pikrat (135 bis 136"C) liegt bei 135"C.After adding ether, 51.1 mg of yellow picrate precipitate. After falling over from glacial acetic acid / ether, the melting point is 134 to 135 "C, the mixed melting point with DL-proline picrate (135 to 136 "C) is 135" C.
Beispiel 3 4,87 g oc-Keto-8-amino-valeriansäure-hydrochlorid, gelöst in 30 ccm Wasser, werden nach Zusatz von 500 mg 300/0ihr Palladiumkohle in der Schüttelbirne hydriert. Nach 2 Stunden kommt die Wasserstoffaufnahme nach einem Verbrauch von 0,5 1 Wasserstoff zum Stillstand. Example 3 4.87 g of oc-keto-8-aminovaleric acid hydrochloride, dissolved in 30 ccm of water, after adding 500 mg of 300/0 of palladium carbon in a shaking pear hydrogenated. After 2 hours, the hydrogen uptake comes after consumption of 0.5 1 hydrogen to a standstill.
Die filtrierte Lösung wird mit 5,8 g frisch gefälltem Silberoxyd über Nacht geschüttelt, filtriert, der Silberoxydüberschuß mit Schwefelwasserstoff ausgefällt und die Lösung im Rotationsverdampfer bis zur Kristallisation eingeengt. Man erhält 2,9 g eines weißgelben Rückstandes. The filtered solution is mixed with 5.8 g of freshly precipitated silver oxide Shaken overnight, filtered, the excess silver oxide with hydrogen sulfide precipitated and the solution concentrated in a rotary evaporator until crystallization. 2.9 g of a white-yellow residue are obtained.
Er wird zusammen mit 5,3 g Pikrinsäure in 10 ccm Eisessig heiß gelöst, abgekühlt und das Pikrat mit Äther ausgefällt. Man erhält 4,8 g des Pikrates, das nach der Umkristallisation aus Wasser bei 134 bis 135"C schmilzt. It is dissolved hot together with 5.3 g of picric acid in 10 ccm of glacial acetic acid, cooled and the picrate precipitated with ether. 4.8 g of the picrate are obtained after recrystallization from water at 134 to 135 "C melts.
Mischschmelzpunkt mit reinem DL-Prolin-Pikrat (Schmelzpunkt 134 bis 135"C): 134 bis 135"C. Mixed melting point with pure DL-proline picrate (melting point 134 to 135 "C): 134 to 135" C.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEM46764A DE1166783B (en) | 1960-10-07 | 1960-10-07 | Process for the production of DL-proline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEM46764A DE1166783B (en) | 1960-10-07 | 1960-10-07 | Process for the production of DL-proline |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1166783B true DE1166783B (en) | 1964-04-02 |
Family
ID=7305698
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEM46764A Pending DE1166783B (en) | 1960-10-07 | 1960-10-07 | Process for the production of DL-proline |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1166783B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5028718A (en) * | 1986-09-12 | 1991-07-02 | Ajinomoto Co., Inc. | Amino acid derivatives, their production and use in preparing carbapenem and carbapenam compounds |
-
1960
- 1960-10-07 DE DEM46764A patent/DE1166783B/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5028718A (en) * | 1986-09-12 | 1991-07-02 | Ajinomoto Co., Inc. | Amino acid derivatives, their production and use in preparing carbapenem and carbapenam compounds |
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