DE968545C - Process for the preparation of bases of the 1-phenyl-2-aminopropane series - Google Patents
Process for the preparation of bases of the 1-phenyl-2-aminopropane seriesInfo
- Publication number
- DE968545C DE968545C DEK25089A DEK0025089A DE968545C DE 968545 C DE968545 C DE 968545C DE K25089 A DEK25089 A DE K25089A DE K0025089 A DEK0025089 A DE K0025089A DE 968545 C DE968545 C DE 968545C
- Authority
- DE
- Germany
- Prior art keywords
- phenyl
- aminopropane
- bases
- series
- preparation
- 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
- 238000000034 method Methods 0.000 title claims description 5
- KWTSXDURSIMDCE-UHFFFAOYSA-N 1-phenylpropan-2-amine Chemical class CC(N)CC1=CC=CC=C1 KWTSXDURSIMDCE-UHFFFAOYSA-N 0.000 title 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 7
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000012433 hydrogen halide Substances 0.000 claims description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 2
- KWGRBVOPPLSCSI-WPRPVWTQSA-N (-)-ephedrine Chemical compound CN[C@@H](C)[C@H](O)C1=CC=CC=C1 KWGRBVOPPLSCSI-WPRPVWTQSA-N 0.000 description 10
- 239000002585 base Substances 0.000 description 7
- KWGRBVOPPLSCSI-UHFFFAOYSA-N d-ephedrine Natural products CNC(C)C(O)C1=CC=CC=C1 KWGRBVOPPLSCSI-UHFFFAOYSA-N 0.000 description 7
- 229960002179 ephedrine Drugs 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 150000001414 amino alcohols Chemical class 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- DLNKOYKMWOXYQA-UHFFFAOYSA-N dl-pseudophenylpropanolamine Natural products CC(N)C(O)C1=CC=CC=C1 DLNKOYKMWOXYQA-UHFFFAOYSA-N 0.000 description 2
- 229960002534 ephedrine hydrochloride Drugs 0.000 description 2
- DLNKOYKMWOXYQA-APPZFPTMSA-N phenylpropanolamine Chemical compound C[C@@H](N)[C@H](O)C1=CC=CC=C1 DLNKOYKMWOXYQA-APPZFPTMSA-N 0.000 description 2
- 229960000395 phenylpropanolamine Drugs 0.000 description 2
- KWGRBVOPPLSCSI-WCBMZHEXSA-N pseudoephedrine Chemical compound CN[C@@H](C)[C@@H](O)C1=CC=CC=C1 KWGRBVOPPLSCSI-WCBMZHEXSA-N 0.000 description 2
- 229960003908 pseudoephedrine Drugs 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DLNKOYKMWOXYQA-CBAPKCEASA-N (-)-norephedrine Chemical compound C[C@H](N)[C@H](O)C1=CC=CC=C1 DLNKOYKMWOXYQA-CBAPKCEASA-N 0.000 description 1
- SOFQDLYSFOWTJX-UHFFFAOYSA-N 1-phenylpropan-2-amine;sulfuric acid Chemical compound OS(O)(=O)=O.CC(N)CC1=CC=CC=C1 SOFQDLYSFOWTJX-UHFFFAOYSA-N 0.000 description 1
- BALXUFOVQVENIU-GNAZCLTHSA-N Ephedrine hydrochloride Chemical compound Cl.CN[C@@H](C)[C@H](O)C1=CC=CC=C1 BALXUFOVQVENIU-GNAZCLTHSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003113 alkalizing effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 1
- ZZGMTCKULVMTDB-CABZTGNLSA-N n-[(1r,2s)-1-hydroxy-1-phenylpropan-2-yl]-n-methylacetamide Chemical compound CC(=O)N(C)[C@@H](C)[C@H](O)C1=CC=CC=C1 ZZGMTCKULVMTDB-CABZTGNLSA-N 0.000 description 1
- OUMBFMLKPJUWDQ-UHFFFAOYSA-N n-benzylpropan-1-amine Chemical compound CCCNCC1=CC=CC=C1 OUMBFMLKPJUWDQ-UHFFFAOYSA-N 0.000 description 1
- MYWUZJCMWCOHBA-UHFFFAOYSA-N n-methyl-1-phenylpropan-2-amine Chemical compound CNC(C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-UHFFFAOYSA-N 0.000 description 1
- CDZOGLJOFWFVOZ-UHFFFAOYSA-N n-propylaniline Chemical compound CCCNC1=CC=CC=C1 CDZOGLJOFWFVOZ-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000006340 racemization Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Die Basen der i-Phenyl^-aminopropanhReihe wurden seither vorzugsweise aus ι-Phenyl-i-halogeru-2-ammopropanen durch Reduktion mit chemischen Reduktionsmittel!» oder durch katalytische Hydrierung gewonnen. Nach einem anderen bekannten ' Verfahren wird z. R i-Pihenyl-2-methylaminop.ropan aus Ephedrin durch Erhitzung mit Jodwasserstoffs äure und' Phosphor hergestellt.The bases of the i-phenyl ^ -aminopropane series have since been preferably made from ι-phenyl-i-halogeru-2-ammopropanes through reduction with chemical reducing agents! " or by catalytic Hydrogenation won. According to another known 'method, for. R i-phenyl-2-methylaminop.ropane from ephedrine by heating with hydriodic acid and phosphorus manufactured.
Es wurde nun gefunden, diaß die i-Phenyl-2-ani'in,opropa)ni-Basen auf einfachste Weise aus den ent sp rechenden ι - Phenyl· - 2 - ami nop rop anolen-(i) 'dadurch hergestellt werden können, daß man auf eine Lösung der Aminoalkohole in Halogenwasserstoffgas enthaltendem Eisessig Wasserstoff in Gegenwart von Palladiummohr als Katalysator einwirken· läßt·. So erhält mam z. B. aus Ephedrin bzw. aus Pseudoephedrin durch Reduktion der Hydroxylgruppe i-Phenyl-2-methylaminopropan, aus Norephedrin oder Norpseudbephedrin i-Phenyli-2-aminopropani. Bei Anwendung der optisch aktiven Aminoalkohole erhält man die entsprechenden optisch aktiven Phenylamino-.propane, jedoch mit umgekehrter optischer Drehung. It has now been found that the i-phenyl-2-ani'in, opropa) ni bases in the simplest way from the corresponding ι - phenyl - 2 - ami nop rop anolen- (i) 'Can be prepared by relying on a solution of the amino alcohols in Glacial acetic acid containing hydrogen halide gas in the presence of palladium black act as a catalyst. So mam z. B. from ephedrine or from pseudoephedrine by reduction the hydroxyl group i-phenyl-2-methylaminopropane, from norephedrine or norpseudbephedrine i-phenyli-2-aminopropane. When applying of the optically active amino alcohols one obtains the corresponding optically active phenylamino-propane, but with reverse optical rotation.
Diese Hydrierungsreaktionen verlaufen mit nahezu quantitativen Ausbeuten; auch tritt bei der Hydrierung der optisch aktiven AminoalkoholeThese hydrogenation reactions proceed with almost quantitative yields; also occurs at the Hydrogenation of the optically active amino alcohols
709 894/8709 894/8
praktisch keine Racemisierung ein: Aus links-Ephedrin bzw. aus rechts-PseudOephedlrm erhält man rechts-Desoxyephedrin, aus links-Norephedrin bzw. aus reehts-Pseudbnorephedrini rechts-Desoxyniorephedriaii. practically no racemization on: off left ephedrine or right-hand pseudoephedrine is obtained from right-hand deoxyephedrine and left-hand norephedrine or from reehts-Pseudbnorephedrini right-Deoxyniorephedriaii.
Es wurde zwar auch schon vorgeschlagen, bei der Herstellung von i-Phenyl-2-methylaminopropan aus i-Phenyl-i-oxy-2-methylaminopropan durch katalytische Reduktion mit Wasserstoff in Gegenwart von Palladium als Katalysator verhältnismäßig große Mengen konzentrierter Schwefelsäure zuzusetzen, welche mit der zu hydrierenden" Substanz eine reaktionstüchtige Molekülverbindung bilden soll (Liebigs Annalen der Chemie, Bd. 560 [1948], S. 219).It has also been suggested for the production of i-phenyl-2-methylaminopropane from i-phenyl-i-oxy-2-methylaminopropane catalytic reduction with hydrogen in the presence of palladium as a catalyst to add large amounts of concentrated sulfuric acid, which with the "substance to be hydrogenated." to form a reactive molecular compound (Liebigs Annalen der Chemie, Vol. 560 [1948], p. 219).
Bei Nachprüfung dieses Verfahrens hat sich jedoch ergeben, daß die Hauptmenge des angewandten Ephedrins in N-Acetylephedrin umgewandelt wird, das bei den angegebenen Reaktionsbedingungen nicht zu i-Phenyl-2-methylaminopropan hydriert wird, so daß das gesuchte Phenylmethylaminopropan nur in sehr geringer Ausbeute erhalten wurde.However, on examination of this method, it was found that the bulk of the Ephedrine is converted into N-acetylephedrine, which under the given reaction conditions does not become i-phenyl-2-methylaminopropane is hydrogenated, so that the phenylmethylaminopropane sought only in very low yield was obtained.
Demgegenüber entsteht nach dem erfindungsgemäßen Verfahren aus Ephedrin unmittelbar in sehr hoher Ausbeute reines i-Phenyl-2-methylaminopropan, was nach den Angaben der vorgenannten Literaturstelle nicht erwartet werden konnte.In contrast, according to the method according to the invention, ephedrine is produced directly in very high yield of pure i-phenyl-2-methylaminopropane, which could not be expected according to the information in the aforementioned literature reference.
Eine Lösung von 60 g razemischem Ephedrinhydrochlorid in 600 ecm Eisessig, der 30 g· Salzsäure-Gas enthält, wird in Gegenwart von 50 g Palladiummohr bei 900 hydlriert. Nach Abtrennung· vom Katalysator wird das Lösungsmittel im Vakuum verdampft, und man erhält nach Alkal'iö'ierung 43 ■g razemische Desoxynorephedrin-Base = 95% der Theorie.A solution of 60 g racemic ephedrine hydrochloride in 600 cc of glacial acetic acid containing 30 g · hydrochloric acid gas is hydlriert in the presence of 50 g of palladium black at 90 0th After the catalyst has been separated off, the solvent is evaporated off in vacuo, and 43 g of racemic deoxynorephedrine base = 95% of theory are obtained after alkali oiling.
In gleicher Weise werden aus 60 g· I-Ephedrinhydrochlorid durch Hydrierung in Salzsäuregas enthaltendem Eisessig mit Palladiummohr als Katalysator 42· g d-Desoxyephedrdn-Base = 96% der Theorie erhalten.In the same way, 60 g of I-ephedrine hydrochloride are made by hydrogenation in glacial acetic acid containing hydrochloric acid gas with palladium black as a catalyst 42 g of d-deoxyephedrine base = 96% of the Theory received.
6b g li-Norephedrip-Base werden in einer Losung von 600 ecm Eisessig, in welchem 46g Salzsäure-Gas enthalten sind', in Gegenwart von 55 g Falladiurorohr hydriert. Die erhaltene,- Base wird nach dem Alkalisieren mit einem organischen Lösungsmittel ausgeschüttelt und darauf in das Sulfa* übergeführt. Man erhält 70 g dtDesoxyoorephedrin-Sulfat mit 'einer Drehung von + 22·,8>° = 95%· der Theorie.6b g of li-norephedrip base are in a solution of 600 ecm of glacial acetic acid, which contains 46 g of hydrochloric acid gas, in the presence of 55 g Falladiurotube hydrogenated. The obtained, - base is shaken out after alkalizing with an organic solvent and then poured into the Sulpha * transferred. 70 g of deoxyoorephedrine sulfate are obtained with 'a rotation of + 22 ·, 8> ° = 95% of theory.
In gleicher Weise erhält man durch Hydrierung von 56 g 1-Norephedrin-hydrochlorid bei . einer Temperatur von 75 bis 850 und Überführung des Reaktionsprodüktes in das schwefelsaure Salz der Base 52 g d-DesoxynorephedWn^sulfat = 95 % ■der Theorie.In the same way, 56 g of 1-norephedrine hydrochloride are obtained by hydrogenating. a temperature of 75 to 85 0 and conversion of the reaction product into the sulfuric acid salt of the base 52 g of d-deoxynorephedWn ^ sulfate = 95% of theory.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEK25089A DE968545C (en) | 1955-03-06 | 1955-03-06 | Process for the preparation of bases of the 1-phenyl-2-aminopropane series |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEK25089A DE968545C (en) | 1955-03-06 | 1955-03-06 | Process for the preparation of bases of the 1-phenyl-2-aminopropane series |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE968545C true DE968545C (en) | 1958-03-06 |
Family
ID=7217210
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEK25089A Expired DE968545C (en) | 1955-03-06 | 1955-03-06 | Process for the preparation of bases of the 1-phenyl-2-aminopropane series |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE968545C (en) |
-
1955
- 1955-03-06 DE DEK25089A patent/DE968545C/en not_active Expired
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