DE870121C - Process for the production of amines - Google Patents
Process for the production of aminesInfo
- Publication number
- DE870121C DE870121C DEK8975A DEK0008975A DE870121C DE 870121 C DE870121 C DE 870121C DE K8975 A DEK8975 A DE K8975A DE K0008975 A DEK0008975 A DE K0008975A DE 870121 C DE870121 C DE 870121C
- Authority
- DE
- Germany
- Prior art keywords
- esters
- ether
- amines
- phenol
- general formula
- 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
- 150000001412 amines Chemical class 0.000 title claims description 4
- 238000000034 method Methods 0.000 title claims description 3
- 150000002148 esters Chemical class 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 150000005215 alkyl ethers Chemical class 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002262 Schiff base Substances 0.000 claims description 3
- 150000004753 Schiff bases Chemical class 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 150000003974 aralkylamines Chemical class 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 150000008379 phenol ethers Chemical class 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- QCCDLTOVEPVEJK-UHFFFAOYSA-N phenylacetone Chemical compound CC(=O)CC1=CC=CC=C1 QCCDLTOVEPVEJK-UHFFFAOYSA-N 0.000 description 4
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 2
- 229910003446 platinum oxide Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- WFWKNGZODAOLEO-UHFFFAOYSA-N 1-(4-Methoxyphenyl)-2-propanone Chemical compound COC1=CC=C(CC(C)=O)C=C1 WFWKNGZODAOLEO-UHFFFAOYSA-N 0.000 description 1
- GKDLTXYXODKDEA-UHFFFAOYSA-N 1-phenylbutan-2-one Chemical compound CCC(=O)CC1=CC=CC=C1 GKDLTXYXODKDEA-UHFFFAOYSA-N 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000036772 blood pressure Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- MDKXBBPLEGPIRI-UHFFFAOYSA-N ethoxyethane;methanol Chemical compound OC.CCOCC MDKXBBPLEGPIRI-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- -1 methoxyphenyl Chemical group 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23C—MILLING
- B23C1/00—Milling machines not designed for particular work or special operations
- B23C1/04—Milling machines not designed for particular work or special operations with a plurality of horizontal working-spindles
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von Aminen Es ist bekannt, daß Amine der allgemeinen Formel worin X und Y Wasserstoff, Alkyl- oder Cycloalkylreste bedeuten, blutdrucksteigernd wirken.Process for the preparation of amines It is known that amines of the general formula where X and Y are hydrogen, alkyl or cycloalkyl radicals, have a blood pressure-increasing effect.
Es wurde nun gefunden, daß durch Einführung eines Aralkylrestes am Stickstoff Verbindungen erhalten werden, die eine Blutdrucksenkung von erheblicher Dauer bewirken und weitgehend von unerwünschten Nebenwirkungen frei sind.It has now been found that by introducing an aralkyl radical on Nitrogen compounds are obtained that lower blood pressure significantly Effect lasting and are largely free of undesirable side effects.
Die neuen Verbindungen werden dadurch hergestellt, daß man i- (4'-Oxyphenyl) -2-aminopropan oder dessen Alkyläther bzw. Ester mit Ketonen oder Aldehyden der allgemeinen Formel R,- CO - R., worin R, Aralkyl und R, Wasserstoff oder niederes Alkyl bedeuten, kondensiert, die erhaltene Schiffsche Base gleichzeitig oder anschließend reduziert und im Falle der Anwendung der Alkyläther bzw. Ester in bekannter Weise zum Phenol verseift.The new compounds are prepared by i- (4'-oxyphenyl) -2-aminopropane or its alkyl ethers or esters with ketones or aldehydes of the general formula R, - CO - R., in which R, aralkyl and R, hydrogen or lower alkyl are condensed, the Schiff base obtained is reduced simultaneously or subsequently and, if the alkyl ethers or esters are used, saponified to give the phenol in a known manner.
Andererseits werden die Verbindungen dadurch erhalten, daß man 4-Oxybenzylmethylketon der Formel bzw. dessen Alkyläther oder Ester mit Aralkylaminen der allgemeinen Formel R, - C H (N H,) - R2 kondensiert und gleichzeitig oder anschließend reduziert, wobei im Falle der Verwendung der Phenoläther oder Ester in bekannter Weise zum Phenol verseift werden muß.On the other hand, the compounds are obtained by using 4-oxybenzyl methyl ketone of the formula or its alkyl ethers or esters with aralkylamines of the general formula R, - C H (N H,) - R2 condensed and simultaneously or subsequently reduced, in which case the phenol ethers or esters must be saponified in a known manner to give the phenol.
Beispiele 1. 26,8 g Benzylmethylketon, 30,7, 9 1- W-OxY-phenyl)-2-aminopropan und o,5 g Platinoxyd in ?,oo ccm Methanol werden bei 3 atÜ 7 Stunden mit Wasserstoff geschüttelt. Darauf wird vom Kataly# sator getrennt, das Lösungsmittel verdampft, der Rückstand mit überschüssigem Ammoniak versetzt und mit Äther bis zur Lösung geschüttelt. Der Äther wird verdampft, der Rückstand in der gleichen Gewichtsmenge Methanol gelöst und bei o' etwa 24 Stunden stehengelassen, worauf man 6,6 g einer Base vom F. 146 bis 147' (aus Methanol) erhält; das Hydro-', chlorid der Base schmilzt bei 213'. Die Base stellt die eine der beiden möglichen stereoisomeren Razemformen von ß- (4-Oxyphenyl) -ß'-phenyl-di-isopropylamin dar.EXAMPLES 1. 26.8 g of benzyl methyl ketone, 30.7, 9 1-W-OxY-phenyl) -2-aminopropane and 0.5 g of platinum oxide in, oo ccm of methanol are shaken with hydrogen at 3 atmospheres for 7 hours. The catalyst is then separated, the solvent is evaporated, excess ammonia is added to the residue and the mixture is shaken with ether until it dissolves. The ether is evaporated, the residue is dissolved in the same amount by weight of methanol and left to stand at 0 'for about 24 hours, whereupon 6.6 g of a base with a melting point of 146 to 147' (from methanol) are obtained; the hydrochloride of the base melts at 213 '. The base represents one of the two possible stereoisomeric racemic forms of ß- (4-oxyphenyl) -ß'-phenyl-di-isopropylamine.
Durch Ansäuern der methanolischen Mutterlauge mit Methanolsalzsäure, Zusatz von Äther bis zur beginnenden Trübung und Stehenlassen bei o' während 24 Stunden erhält man 74 g des Hydrochlorids der anderen stereoisoineren Razemform vom F. 24 bis 215' (aus Methanol-Äther); die Base schmilzt bei iog' (aus Äther).By acidifying the methanolic mother liquor with methanol hydrochloric acid, adding ether until the onset of turbidity and leaving it to stand at o 'for 24 hours, 74 g of the hydrochloride of the other stereoisomeric racemic form with a melting point of 24 to 215' are obtained (from methanol ether); the base melts at iog '(from ether).
Nach Aufaurbeitung der Mutterlange nach den obigen Angaben werden noch weitere Mengen der beiden stereoisomeren Verbindungen erhalten.After working up the mother length according to the above information still further amounts of the two stereoisomeric compounds obtained.
2. 27 g i-Phenyl-g-amü-1o-propan, 33 g 4-Methoxybenzylmethylketon und 0,5 9 Platinoxyd in 2oo ccm Methanol werden bei 3 atü 7 Stunden mit Wasserstoff geschüttelt. Darauf wird vom Katalysator getrennt, das Lösungsmittel verdampft und der Rückstand ohne weitere Reinigung mit 3oo ccm 480/0iger Bromwasserstoffsäure % Stunde unter Rückfluß gekocht. Die Bromwasserstoffsäure wird im Vakuum abgedampft und der Rückstand nach Zusatz von Ammoniak in Äther gelöst. Die weitere Aufarbeitung geschieht nach Beispiel i.2. 27 g of i-phenyl-g-amu-1o-propane, 33 g of 4-methoxybenzyl methyl ketone and 0.5 9 of platinum oxide in 2oo cc of methanol are shaken with hydrogen at 3 atmospheres for 7 hours. It is separated from the catalyst, the solvent evaporated and the residue without further purification with 3oo cc 480 / 0iger hydrobromic cooked% hour under reflux. The hydrobromic acid is evaporated off in vacuo and the residue is dissolved in ether after adding ammonia. The further work-up takes place according to Example i.
3. 1519 1- (4'-Oxyphenyl) -2-aminopropan" 134 9 Benzyhnethyllketon und 48 g 990/,ige Ameisensäure werden ün Ötbad unter Rückfluß 5 Stunden zum Sieden erhitzr. Das Reaktionsprodukt wird mit Ammoniak vesetzt und mit Äther geschüttelt, der Ätherrückstand in der gleichen Gewichtsmenge Methanol gelöst und bei - o' 24 Stunden stehengelassen, worauf man 52 g Base vom F. 147' erhält. Durch Ansäuern der Mutterlauge Mit Methanolsalzsäure und Versetzen mit Äther erhält man 7o g des Hydrochlorids VOM F. 214 bis 215' der bei iog' schmelzenden Base. Durch Aufarbeiten der Mutterlauge erhält man weitere 7,g Base vom F. 147' und 21 g Hydr.ochlorid VOM F. 214 bis 21:5'. 4. 165 9 1- (4#-Methoxyphenyl) -2-aminopropan, 134 9 Benzylmethylketon und 48 9 9911/0ige Ameisensäure werden im Ölbad unter Rückfluß 4 bis 5 Stunden erhitzt. Darauf wird mit überschüssiger Natronlauge versetzt, in Äther gelöst und der Ätherrückstand im Gewicht von ?,gi g im Vakuum destilliert, wobei man bei Kp", 172 bis :[8o' 241 g Base erhält. Man erhitzt das Destillat mit überschüssiger 480/(,iger Bromwasserstoffsäure 3/" Stunde unter Rückfluß, verdampft die Bromwasserstoffsäure im Vakuum, versetzt den Rückstand mit Ammoniak und nimmt in Äther auf. Die weitere Aufarbeitung erfolgt wie in den Beispielen i und 3, und Man erhält 45 g Base vom F. 147' und 81 g des Hydrochlorids vom F.'-14 bis 215'. 3. 151 9 1- (4'-oxyphenyl) -2-aminopropane "134 9 benzyl ethyl ketone and 48 g 990% formic acid are heated to boiling in an oil bath under reflux for 5 hours. The reaction product is treated with ammonia and shaken with ether, the ether residue is dissolved in an equal weight of methanol and, at -. acidification 'stand for 24 hours whereupon 52 g of base, mp 147' o receives the mother liquor with methanol hydrochloric acid and addition of ether to 7o g of the hydrochloride, melting at 214 receives up . 215 'at the iog' melting Base by working up the mother liquor obtained additional 7 g of base, mp 147 'and 21 g Hydr.ochlorid mp 214-21: 5' 4. 165 9 1- (4 #. methoxyphenyl) -2-aminopropane, 134 9 benzyl methyl ketone and 48 9 9911 / 0ige formic acid are heated in an oil bath at reflux for 4 to 5 hours. Then is added with an excess of sodium hydroxide, dissolved in ether and the ether residue in weight of?, gi g in Vacuum distilled, with bp ", 172 to: [8o '241 g Bas e receives. The distillate is refluxed with an excess of 480% hydrobromic acid for 3½ hour, the hydrobromic acid is evaporated off in vacuo, the residue is treated with ammonia and taken up in ether. Further work-up is carried out as in Examples 1 and 3, and Man receives 45 g of base from F. 147 'and 81 g of the hydrochloride from F. 14 to 215'.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEK8975A DE870121C (en) | 1951-02-12 | 1951-02-13 | Process for the production of amines |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE303459X | 1951-02-12 | ||
| DEK8975A DE870121C (en) | 1951-02-12 | 1951-02-13 | Process for the production of amines |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE870121C true DE870121C (en) | 1953-03-09 |
Family
ID=25787829
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEK8975A Expired DE870121C (en) | 1951-02-12 | 1951-02-13 | Process for the production of amines |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE870121C (en) |
-
1951
- 1951-02-13 DE DEK8975A patent/DE870121C/en not_active Expired
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