DE585667C - Process for the production of levorotatory aminopropanols - Google Patents
Process for the production of levorotatory aminopropanolsInfo
- Publication number
- DE585667C DE585667C DEK119837D DEK0119837D DE585667C DE 585667 C DE585667 C DE 585667C DE K119837 D DEK119837 D DE K119837D DE K0119837 D DEK0119837 D DE K0119837D DE 585667 C DE585667 C DE 585667C
- Authority
- DE
- Germany
- Prior art keywords
- levorotatory
- production
- aminopropanols
- hydrochloride
- alcohol
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- MXZROAOUCUVNHX-UHFFFAOYSA-N 2-Aminopropanol Chemical class CCC(N)O MXZROAOUCUVNHX-UHFFFAOYSA-N 0.000 title description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- ZBFFNPODXBJBPW-SECBINFHSA-N (S)-phenylacetylcarbinol Chemical compound CC(=O)[C@@H](O)C1=CC=CC=C1 ZBFFNPODXBJBPW-SECBINFHSA-N 0.000 claims 1
- 150000001414 amino alcohols Chemical class 0.000 claims 1
- 239000003638 chemical reducing agent Substances 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000000855 fermentation Methods 0.000 description 4
- 230000004151 fermentation Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000010626 work up procedure Methods 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 2
- SATCULPHIDQDRE-UHFFFAOYSA-N piperonal Chemical compound O=CC1=CC=C2OCOC2=C1 SATCULPHIDQDRE-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- -1 l-i- (p-methoxyphenyl) -2-methylaminopropan-i-ol Chemical compound 0.000 description 1
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 description 1
- 229940081310 piperonal Drugs 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical class CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Durch Patent 548459 ist die HerstellungBy patent 548459 the manufacture is
von 1-1 -Phenyl-a-methylaminopropaa-1 -öl durch Reduktion von linksdrehendem Phenylpropanolon in Gegenwart von Methylamin geschützt. of 1-1 phenyl-a-methylaminopropaa-1 oil protected by reduction of levorotatory phenylpropanolone in the presence of methylamine.
Es wurde gefunden, daß nach diesem Verfahren sich ganz allgemein linksdrehende Aminopropanole herstellen lassen, indem man linksdrehende Ketale der FormelIt has been found that, according to this process, left-handed ones are quite generally left-handed Aminopropanols can be produced by adding levorotatory ketals of the formula
R-CH(OH)-CO-CH3 R-CH (OH) -CO-CH 3
in Gegenwart von Aminen der Reduktion unterwirft. R kann in diesem Falle ein beliebiger
aliphatischer, aromatischer oder heterocyclischer Rest oder dessen Substitutionsprodukt
sein. Ausgenommen ist jedoch die Umsetzung von links drehenden m- oder p-i-Oxypbenyl-2-ketopropan-i-olen,
welche bereits Gegenstand des älteren Patents 571 229 ist.
Die Darstellung der optisch aktiven Propanole erfolgt z. B. durch Vergärung der entsprechenden
Aldehyde nach dem Verfahren von N e.u b e r g (Biochemische Zeitschrift 115
[1921] S. 282).subjected to reduction in the presence of amines. In this case, R can be any desired aliphatic, aromatic or heterocyclic radical or its substitution product. However, the conversion of counter-clockwise m- or pi-oxypbenyl-2-ketopropan-i-ols, which is already the subject of the earlier patent 571,229, is excluded.
The representation of the optically active propanols takes place z. B. by fermentation of the corresponding aldehydes according to the method of N eu berg (Biochemische Zeitschrift 115 [1921] p. 282).
100 g l-i-Phenylpropan-i-ol-2-on werden in 750 ecm Äther gelöst und mit 125 g 33°/oiger wäßriger Äthylaminlösung 1J2 Stundte geschüttelt, wobei unter Wärmeentwicklung Kondensation stattfindet. Das Reaktionsgemisch versetzt man anschließend unter Rühren mit 200 ecm Methylalkohol und 75 g aktiviertem Aluminium. Die dabei stark einsetzende Reaktion muß durch Kühlung gemäßigt werden. Nach beendigter Reduktion wird der filtrierten alkoholisch-ätherischen Lösung die entstandene Base mit verdünnter Säure entzogen. Die weitere Aufarbeitung erfolgt in bekannter Weise. Das Hydrochlorid des l-i-Phenyl-2-äthylaminopropan-i-ol kristallisiert aus Alkohol in farblosen Blättchen vom F. 220°. Eine io°/0ige wäßrige Lösung des Salzes dreht im 1 dm-Rohr bei 20° C, 2,12° nach links.100 g li-phenylpropane-i-ol-2-one are dissolved in 750 cc of ether and shaken with 125 g of 33 ° / o aqueous Äthylaminlösung 1 J 2 Stundte, wherein taking place with evolution of heat condensation. The reaction mixture is then mixed with 200 ecm of methyl alcohol and 75 g of activated aluminum while stirring. The reaction that sets in strongly here must be moderated by cooling. When the reduction is complete, the base formed is removed from the filtered alcoholic-ethereal solution using dilute acid. The further work-up takes place in a known manner. The hydrochloride of li-phenyl-2-ethylaminopropan-i-ol crystallizes from alcohol in colorless leaves with a melting point of 220 °. A io ° / 0 aqueous solution of the salt rotates in 1 dm-tube at 20 ° C, 2.12 ° to the left.
120 g· des durch Ätherauszug gewonnenen 1-phenylpropanolonhaltigen Gärungsproduktes (etwa 2J10 Mol Ketol enthaltend, vgl. Biochemische Zeitschrift 115 [1921] S. 282) läßt man ohne weitere Reinigung in eine Lösung von 50 g Nonylamin in 500 ecm Äther in Gegenwart von 30 g aktiviertem Aluminium unter Rühren im Verlauf von 2 Stunden eintropfen. Gleichzeitig gibt man 30 g Wasser tropfenweise' hinzu. Die heftige Reaktion120 g · of the 1-phenylpropanolone-containing fermentation product obtained by extracting ether ( containing about 2 J 10 mol of ketol, cf. Biochemische Zeitschrift 115 [1921] p. 282) are left without further purification in a solution of 50 g of nonylamine in 500 ecm of ether in the presence of 30 g of activated aluminum are added dropwise with stirring over the course of 2 hours. At the same time, 30 g of water are added dropwise. The violent reaction
wird durch Kühlung gemäßigt. Die Aufarbeitung geschieht wie bei Beispiel i. Das 1-i-Pheinyl-2-nonylamniopropan-i-ol destilliert als stark lichtbrechendes öl vom Kp8193 bis 195 °. Das in Wasser schwer lösliche Hydrochlorid kristallisiert aus Alkohol in derben perlmutterglänzenden Schuppen vom F. 219 bis 2200. Die 5%ige absolut alkoholische Lösung des Hydrochlorids dreht im 2 dm-Rohr bei 200 0,94° nach links.is tempered by cooling. The work-up is carried out as in Example i. The 1-i-phenyl-2-nonylamniopropan-i-ol distills as a strongly light-refracting oil with a boiling point of 8 193 to 195 °. The hydrochloride, which is sparingly soluble in water, crystallizes from alcohol in coarse pearlescent flakes with a mp of 219 to 220 ° . The 5% absolute alcoholic solution of the hydrochloride rotates in a 2 dm-tube at 20 0 0.94 ° to the left.
Bei sp i-el 3At game 3
125 g des durch Gärung aus Anisaldehyd erhaltenen Rohketols, enthaltend etwa 30 bis 40% l-i-(p-Methoxyphenyl)-propan-i-ol-2-on, werden in 250 ecm Äther gelöst und in Gegenwart von 15 g Methylamin mit 100 ecm i°/oiger kolloidaler Platinlösung der katalytischen Reduktion unterworfen. Nach beendigter Wasser-Stoffaufnahme wird in bekannter Weise aufgearbeitet. 125 g of the crude ketol obtained by fermentation from anisaldehyde, containing about 30 to 40% li- (p-methoxyphenyl) propan-i-ol-2-one, are dissolved in 250 ecm of ether and in the presence of 15 g of methylamine at 100 ecm i ° / o sodium subjected colloidal platinum solution to catalytic reduction. After the uptake of water has ceased, it is worked up in a known manner.
Das Hydrochlorid des l-i-(p-Methoxyphenyl)-2-methylaminopropan-i-ols kristallisiert aus Alkohol in derben Prismen vomThe hydrochloride of l-i- (p-methoxyphenyl) -2-methylaminopropan-i-ol crystallized from alcohol in coarse prisms from
9.5 F. 2470. 0,6333 g Substanz in 10,25 g Wasser "gelöst drehen im 1 dm-Rohr bei 20° C diePor larisationsebene um i,8° nach links. 9.5 F. 247 0 . 0.6333 g of substance dissolved in 10.25 g of water "turn the por larization plane by 1.8 ° to the left in the 1 dm tube at 20 ° C.
250 g durch Gärung von Piperonal gewonnenes Rohketol, enthaltend etwa 35°/0 1-1 - (3, 4-Methylendioxyphenyl) -propan-i-ol-2-on werden mit 30 g Methylamin und 200 ecm i°/oiger kolloidaler Platinlösung katalytisch reduziert. DieAufarbeitungerfolgtwieunterBeispiel 3. Das Hydrochlorid des I-i- (3,4-Methylendioxyphenyl) -2-methylaminopropan-i-ols erhält man aus Alkohol in kleinen derben Prismen vom F. 225 °. Die Linksdrehung der 10 °/oigen wäßrigen Lösung beträgt im 1 dm-Rohr bei 20 ° 2,7°.250 g of fermented piperonal Rohketol obtained, containing about 35 ° / 0 1-1 - (3, 4-methylenedioxyphenyl) propan-i-ol-2-one with 30 g of methylamine, and 200 cc i ° / o hydrochloric colloidal Catalytically reduced platinum solution. The work-up is carried out as in Example 3. The hydrochloride of Ii- (3,4-methylenedioxyphenyl) -2-methylaminopropan-i-ol is obtained from alcohol in small, coarse prisms with a melting point of 225 °. The counterclockwise rotation of the 10% aqueous solution in the 1 dm tube at 20 ° is 2.7 °.
Das durch Vergären von Furfurol erhaltene l-i-Furylpropan-i-ol-2-on wird wie in Beispiel ι oder 3 in Gegenwart von Methylamin reduziert. Das Hydrochlorid des 1-l-Furyl-2-methylaminopropan-i-ol kristallisiert aus Ätheralkohol als feines weißes Kristallpulver vom F. 1300. Eine io°/0ige wäßrige Lösung dreht im 1 dm-Rohr bei 190 0,97° nach links.The li-furylpropan-i-ol-2-one obtained by fermentation of furfural is reduced as in Example 1 or 3 in the presence of methylamine. The hydrochloride of 1-l-furyl-2-methylaminopropane-i-ol crystallized from ether-alcohol as a fine white crystalline powder, melting at 130 0th A io ° / 0 aqueous solution rotates in 1 dm-tube at 19 0 0.97 ° to the left.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEK119837D DE585667C (en) | 1931-04-05 | 1931-04-05 | Process for the production of levorotatory aminopropanols |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEK119837D DE585667C (en) | 1931-04-05 | 1931-04-05 | Process for the production of levorotatory aminopropanols |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE585667C true DE585667C (en) | 1933-10-06 |
Family
ID=7244437
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEK119837D Expired DE585667C (en) | 1931-04-05 | 1931-04-05 | Process for the production of levorotatory aminopropanols |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE585667C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE767193C (en) * | 1938-01-20 | 1952-02-14 | Theodor H Temmler | Process for the preparation of amino compounds |
-
1931
- 1931-04-05 DE DEK119837D patent/DE585667C/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE767193C (en) * | 1938-01-20 | 1952-02-14 | Theodor H Temmler | Process for the preparation of amino compounds |
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