DE871155C - Process for the preparation of N-Monomethyl-ª-phenylethylamines - Google Patents
Process for the preparation of N-Monomethyl-ª-phenylethylaminesInfo
- Publication number
- DE871155C DE871155C DET3002D DET0003002D DE871155C DE 871155 C DE871155 C DE 871155C DE T3002 D DET3002 D DE T3002D DE T0003002 D DET0003002 D DE T0003002D DE 871155 C DE871155 C DE 871155C
- Authority
- DE
- Germany
- Prior art keywords
- phenylethylamines
- parts
- preparation
- formaldehyde
- monomethyl
- 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
- 238000002360 preparation method Methods 0.000 title claims description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000008098 formaldehyde solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 125000002183 isoquinolinyl group Chemical class C1(=NC=CC2=CC=CC=C12)* 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- DBJNWDVLSZLQOL-UHFFFAOYSA-N n-methyl-n-propan-2-ylaniline Chemical compound CC(C)N(C)C1=CC=CC=C1 DBJNWDVLSZLQOL-UHFFFAOYSA-N 0.000 description 2
- SASNBVQSOZSTPD-UHFFFAOYSA-N n-methylphenethylamine Chemical class CNCCC1=CC=CC=C1 SASNBVQSOZSTPD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 description 2
- KDFDOINBXBEOLZ-UHFFFAOYSA-N 2-phenylpropan-2-amine Chemical compound CC(C)(N)C1=CC=CC=C1 KDFDOINBXBEOLZ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- KZBODYTXULRMBT-UHFFFAOYSA-N [Ba].[Pt] Chemical compound [Ba].[Pt] KZBODYTXULRMBT-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- -1 dimethyl compound Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- FRCFWPVMFJMNDP-UHFFFAOYSA-N n-propan-2-ylaniline Chemical compound CC(C)NC1=CC=CC=C1 FRCFWPVMFJMNDP-UHFFFAOYSA-N 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 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
- C07C213/02—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 involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
Verfahren zur Herstellung von N-Monomethyl-ß-phenyläthylaminen Es sind bereits Methoden zur Herstellung von N-Monomethylphenyläthylaminen bekannt. Bei diesen Bildungsweisen erhält man entweder die N-Monomethylphenyläthylamine nicht in einerAusbeute, wie sie bei technischen Verfahren verlangt werden muh, oder die Herstellung erfolgt in mehreren Stufen.Process for the preparation of N-monomethyl-ß-phenylethylamines Es Methods for the preparation of N-monomethylphenylethylamines are already known. With these modes of formation, either the N-monomethylphenylethylamines are not obtained in a yield as required in technical processes, or the Production takes place in several stages.
Es ist ferner bekannt, ß-Phenyläthylamine durch Behandeln mit Formaldehyd in Isochinolinderivate überzuführen. Dabei ist es gleichgültig, ob es sich um das ß-Phenyläthylamin selbst oder um seine N- bzw. C-Homologen handelt. Ausschlaggebend ist, daß die Aminogruppe in ß-Stellung zum Phenylkern steht und daß der Phenylkern keine Oxy- bzw. Alkoxygruppen enthält, da in diesen Fällen ein Ringschluß zum Isochinolinderivat nur sehr schwer eintritt bzw. nur in verschwindendem Umfang stattfindet.It is also known to treat ß-phenylethylamines with formaldehyde to be converted into isoquinoline derivatives. It does not matter whether it is that ß-Phenylethylamine itself or its N or C homologues. Decisive is that the amino group is in ß-position to the phenyl nucleus and that the phenyl nucleus contains no oxy or alkoxy groups, since in these cases a ring closure to the isoquinoline derivative occurs only with great difficulty or takes place only to a negligible extent.
Es ist auch nicht mehr neu, mit Formaldehyd im Überschuß in Gegenwart reduzierend wirkender Stoffe eine Methylierung am Stickstoff sekundärer und primärer Amine durchzuführen. Dabei entsteht auch im letzteren Fall vorwiegend oder ausschließlich die tertiäre Dimethylverbindung.It's also no longer new, with excess formaldehyde in the presence substances with a reducing effect cause methylation on the nitrogen of secondary and primary To carry out amines. In the latter case, too, occurs predominantly or exclusively the tertiary dimethyl compound.
Es wurde nun gefunden, daß man ohne Ringschluß zum Isochinolinderivat und unter Vermeidung der Bildung tertiärer Amine zu monomethylierten ß-Phenyläthylaminen gelangen kann, wenn man ß-Phenyläthylamine der allgemeinen Formel worin R1, R2, R3 und R4 Wasserstoff oder solche Radikale bedeuten, die unter den gegebenen Bedingungen mit Formaldehyd nicht zu reagieren vermögen, mit etwa i Mol Formaldehyd kondensiert und gleichzeitig oder anschließend in Abwesenheit von Säuren reduziert.It has now been found that it is possible to obtain monomethylated ß-phenylethylamines without ring closure to the isoquinoline derivative and avoiding the formation of tertiary amines if ß-phenylethylamines of the general formula are used where R1, R2, R3 and R4 are hydrogen or radicals which are unable to react with formaldehyde under the given conditions, condensed with about 1 mol of formaldehyde and simultaneously or subsequently reduced in the absence of acids.
Beispiele 1. 136 Teile ,d, 1-Phenylisopropylarnin werden in 35o Teilen einer alkoholischen Lösung, die i Mol Formaldehydlösung enthält, nach Zugabe von mehr als der berechneten Menge aktiviertem Aluminium unter mehrstündigem Erwärmen reduziert. Gegen Schluß der Reduktion wird die Reaktion durch Zugabe von Wasser zu Ende geführt. Aus dem Filtrat vom Aluminiumhydroxyd wird nach Eindampfen der angesäuerten Lösung mittels Alkali das Phenyl-N-methylisopropylamin vom Kp.o 95° erhalten. Das Hydrochlorid schmilzt bei iq.o°.Examples 1. 136 parts, d, 1-phenylisopropylamine are in 35o parts an alcoholic solution containing one mole of formaldehyde solution after adding more than the calculated amount of activated aluminum with heating for several hours reduced. Towards the end of the reduction, the reaction is stopped by adding water brought to the end. After evaporation, the aluminum hydroxide is the filtrate acidified solution by means of alkali the phenyl-N-methylisopropylamine with a boiling point of 95 ° obtain. The hydrochloride melts at iq.o °.
2. 7 o Teile rechtsdrehendes Phenylisopropylamin werden nach Zugabe von Zoo Teilen Alkohol sowie ,der li Mol entsprechenden Menge wäß.riger Formaldehydlösun:g mittels. aktiviertenAlumnniums unter ständigem Rühren und Erwärmen reduziert. Aus dem Filtrat vom Aluminiumhydroxyd wird das Phosphat des rechtsdrehenden N-Methyl-phenylisopropylamin erhalten. Es schmilzt nach Umkristallisieren aus Methanol bei i97°.2. 7 o parts of dextrorotatory phenylisopropylamine are added after addition von Zoo parts of alcohol and the corresponding amount of aqueous formaldehyde solution: g by means of. activated aluminum with constant stirring and heating. the end The phosphate of the dextrorotatory N-methyl-phenylisopropylamine becomes the filtrate from the aluminum hydroxide obtain. After recrystallization from methanol, it melts at i97 °.
3. 8o Teile linksdrehendes i-Phenyl-2-aminopropanol-(i) werden in 25o Teilen Alkohol gelöst und nach Zusatz der i Mol entsprechenden Menge Formaldehydlösung sowie etwas mehr als der berechneten Menge aktiven Aluminiums mehrere Stunden erwärmt, wobei für lebhafte Durchmischung gesorgt wird. Die Reaktion wird gegebenenfalls durch Zusatz von Wasser zu Ende geführt. Sodann wird vom Aluminiumhydroxyd abfiltriert und das Filtrat mit Salzsäure neutralisiert. Nach Verdampfen des Alkohols wird der Rückstand aus Alkohol umkristallisiert und so das Hydrochlorid des i-Phenyl-2-methylaminopropanols-(i) vom Schmelzpunkt 21q.° erhalten. q.. 3o Teile i-Phenyl-i-inethyl-2-aminoäthan werden in i oo Teilen Methylalkohol gelöst und nach Zusatz von i Mol Formaldehyd sowie o,5 Teilen Palladium-Mohr hydriert. Nach Aufnahme von i Mol Wasserstoff wird vom Katalysator abfiltriert und das mit Salzsäure neutralisierte Filtrat zur Trockne gedampft. Der Rückstand wurde in Wasser aufgenommen, mit Kohle filtriert und mit Alkali die Base in Freiheit gesetzt. Bei 16 mm ging das i-Phenyl-i-methyl-2-methylaminoäthan bei 96 bis 99° über.3. 80 parts of levorotatory i-phenyl-2-aminopropanol- (i) are used in Dissolved 250 parts of alcohol and, after the addition of the corresponding amount of formaldehyde solution, one mole as well as a little more than the calculated amount of active aluminum heated for several hours, whereby a lively mix is ensured. The reaction is optional completed by adding water. The aluminum hydroxide is then filtered off and the filtrate is neutralized with hydrochloric acid. After the alcohol has evaporated, the Recrystallized residue from alcohol and so the hydrochloride of i-phenyl-2-methylaminopropanols- (i) obtained from melting point 21q. °. q .. 3o parts of i-phenyl-i-ynethyl-2-aminoethane dissolved in i oo parts of methyl alcohol and, after the addition of i mol of formaldehyde, as well 0.5 parts of palladium black hydrogenated. After uptake of 1 mole of hydrogen is from The catalyst is filtered off and the filtrate neutralized with hydrochloric acid to dryness steamed. The residue was taken up in water, filtered with charcoal and washed with Alkali set the base free. The i-phenyl-i-methyl-2-methylaminoethane went at 16 mm at 96 to 99 ° above.
5. 8o Teile i-Phenyl-2-aminobutan werden in Zoo Teilen Alkohol gelöst und nach Zusatz der i Mol entsprechenden Menge wäßri:ger Formaldehydlösung sowie eines Platin-Barium,sulfat-Kat.alysators ;hydriert. Nach Aufnahme derfür i Mol berechneten Menge Wasserstoff wird vom Katalysator abfiltriert und das mit Salzsäure neutralisierte Filtrat im Vakuum zur Trockne gedampft. Der Rückstand wird in Wasser aufgenommen, die mit Kohle filtrierte Lösung wird alkalisch gemacht, ausgeäthert und getrocknet. Nach Abdampfen des Äthers wird das i-Phenyl-2-methylaminobutan vom Kp" io5° erhalten.5. 80 parts of i-phenyl-2-aminobutane are dissolved in zoo parts of alcohol and after the addition of the i mol corresponding amount of aqueous formaldehyde solution and of a platinum-barium, sulfate catalyst; hydrogenated. After including the calculated for 1 mole Amount of hydrogen is filtered off from the catalyst and neutralized with hydrochloric acid The filtrate was evaporated to dryness in vacuo. The residue is taken up in water, the solution, filtered with charcoal, is made alkaline, etherified and dried. After evaporation of the ether, the i-phenyl-2-methylaminobutane is obtained with a boiling point of 10 °.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DET3002D DE871155C (en) | 1938-05-25 | 1938-05-25 | Process for the preparation of N-Monomethyl-ª-phenylethylamines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DET3002D DE871155C (en) | 1938-05-25 | 1938-05-25 | Process for the preparation of N-Monomethyl-ª-phenylethylamines |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE871155C true DE871155C (en) | 1953-03-19 |
Family
ID=7544153
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DET3002D Expired DE871155C (en) | 1938-05-25 | 1938-05-25 | Process for the preparation of N-Monomethyl-ª-phenylethylamines |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE871155C (en) |
-
1938
- 1938-05-25 DE DET3002D patent/DE871155C/en not_active Expired
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