CH638487A5 - Novel substituted di(phenylethyl)amines - Google Patents
Novel substituted di(phenylethyl)amines Download PDFInfo
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- CH638487A5 CH638487A5 CH680382A CH680382A CH638487A5 CH 638487 A5 CH638487 A5 CH 638487A5 CH 680382 A CH680382 A CH 680382A CH 680382 A CH680382 A CH 680382A CH 638487 A5 CH638487 A5 CH 638487A5
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
- C07D223/14—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D223/16—Benzazepines; Hydrogenated benzazepines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/27—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups
- C07C205/32—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups bound to acyclic carbon atoms and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/70—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
- C07C45/71—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form being hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
- C07C47/575—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing ether groups, groups, groups, or groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
- C07D303/22—Ethers with hydroxy compounds containing no oxirane rings with monohydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/04—Ortho-condensed systems
Abstract
Description
Die Erfindung betrifft die im Anspruch 1 definierten neuen Verbindungen der allgemeinen Formel I, die als Zwi- 35 schenprodukte zur Herstellung pharmakologisch aktiver Benzazepinverbindungen wertvoll sind. The invention relates to the new compounds of general formula I defined in claim 1, which are valuable as intermediates for the preparation of pharmacologically active benzazepine compounds.
Die Verbindungen der Formel I lassen sich nach den Verfahren der US-PS 3 211 792,3 869 474 und 3 804 839 oder nach Chem. Abst., Bd. 80,95 398 oder nach den Ver- 40 fahren der folgenden Beispiele herstellen. The compounds of the formula I can be prepared by the processes of US Pat. Nos. 3,211,792,3 869,474 and 3,804,839 or by Chem. Abst., Vol. 80.95 398 or by the processes of the following examples.
Die Verbindungen der allgemeinen Formel I werden zweckmässigerweise durch Erwärmen von äquimolaren Mengen eines Styroloxids mit 3,4-Dialkoxyphenäthylamin, das entweder bekannt ist oder nach bekannten Verfahren 45 hergestellt werden kann, wobei beide Reaktionsteilnehmer in entsprechender Weise substituiert sein können, entweder allein oder in einem inerten organischen Lösungsmittel, wie Tetrahydrofuran, hergestellt. Vorzugsweise wird die Erwärmung 12 bis 24 Stunden auf einem Dampfbad oder bei der so Rückflusstemperatur durchgeführt. Das erforderliche Styroloxid wird zweckmässigerweise durch Umsetzung des Ylid-Derivats von Natriumhydrid und Trimethylsulfonium-jodid mit dem entsprechend substituierten Benzaldehyd hergestellt. 55 Die Beispiele erläutern die Erfindung. The compounds of general formula I are conveniently obtained by heating equimolar amounts of a styrene oxide with 3,4-dialkoxyphenethylamine, which is either known or can be prepared by known methods 45, both of which can be substituted in a corresponding manner, either alone or in one inert organic solvents such as tetrahydrofuran. The heating is preferably carried out for 12 to 24 hours on a steam bath or at the reflux temperature. The styrene oxide required is expediently prepared by reacting the ylide derivative of sodium hydride and trimethylsulfonium iodide with the appropriately substituted benzaldehyde. 55 The examples illustrate the invention.
Beispiel 1 example 1
Ein Gemisch aus 100 g (0,55 Mol) 3,4-DimethoxyphenyI-äthylamin und 66,2 g (0,55 Mol) Styroloxid in 200 ml Tetrahydrofuran wird über Nacht unter Rückfluss erwärmt. Sodann wird das Lösungsmittel unter vermindertem Druck abgedampft. Der Rückstand wird mit etwa 500 ml n-Butyl-chlorid versetzt. Das Gemisch wird leicht gekühlt. Nach Filtration erhält man N-[2-(3,4-Dimethoxyphenyl)-äthyl]-2-phenyl-2-hydroxyäthylamin vom F. 92-93 °C. A mixture of 100 g (0.55 mol) of 3,4-dimethoxyphenyI-ethylamine and 66.2 g (0.55 mol) of styrene oxide in 200 ml of tetrahydrofuran is heated under reflux overnight. The solvent is then evaporated off under reduced pressure. About 500 ml of n-butyl chloride are added to the residue. The mixture is cooled slightly. After filtration, N- [2- (3,4-dimethoxyphenyl) ethyl] -2-phenyl-2-hydroxyethylamine of melting point 92-93 ° C. is obtained.
71,5 g (0,238 Mol) dieses Phenäthylamins werden in 400 ml Essigsäure gelöst. Diese Lösung wird gekühlt. So60 71.5 g (0.238 mol) of this phenethylamine are dissolved in 400 ml of acetic acid. This solution is cooled. So60
65 65
dann wird die Lösung innerhalb von 30 bis 45 Minuten mit 16,9 g (0,238 Mol) Chlorgas versetzt. Anschliessend wird das Reaktionsgemisch in Wasser gegossen, mit einer 40pro-zentigen Natriumhydroxidlösung alkalisch gemacht und unter Rühren mit etwa 250 ml Diäthyläther versetzt. Der erhaltene Feststoff wird abfiltriert. Man erhält N-[2-(2-Chlor-4,5-dimethoxyphenyI)-äthyl}-2-phenyl-2-hydroxyäthy!amin vom F. 110-113°C. then 16.9 g (0.238 mol) of chlorine gas are added to the solution within 30 to 45 minutes. The reaction mixture is then poured into water, made alkaline with a 40 percent sodium hydroxide solution, and about 250 ml of diethyl ether are added with stirring. The solid obtained is filtered off. N- [2- (2-chloro-4,5-dimethoxyphenyl) ethyl} -2-phenyl-2-hydroxyethyl! Amine of mp 110-113 ° C. is obtained.
Beispiel 2 Example 2
200 g (1,32 Mol) Isovanillin werden in 1200 ml Chloroform suspendiert. Sodann werden 103 g (1,45 Mol) Chlor, gelöst in Tetrachlorkohlenstoff, in 3 Anteilen von je 500 ml zugegeben. Die Suspension wird während der Zugabe heftig gerührt. Dabei wird die Reaktion mit einem Wasserbad auf etwa 25 °C gehalten. Die Suspension wird 22 Minuten nach beendeter Chlorzugabe gerührt. Der Niederschlag wird abfiltriert, aus Methanol kristallisiert und aus Isopropanol/ Essigsäureäthylester umkristallisiert. Man erhält 98,7 g (40 Prozent d.Th.) 2-Chlor-3-hydroxy-4-methoxybenzaldehyd vom F. 204-206 °C. 200 g (1.32 mol) of isovanillin are suspended in 1200 ml of chloroform. 103 g (1.45 mol) of chlorine, dissolved in carbon tetrachloride, are then added in 3 portions of 500 ml each. The suspension is stirred vigorously during the addition. The reaction is kept at about 25 ° C. with a water bath. The suspension is stirred 22 minutes after the addition of chlorine has ended. The precipitate is filtered off, crystallized from methanol and recrystallized from isopropanol / ethyl acetate. 98.7 g (40 percent of theory) of 2-chloro-3-hydroxy-4-methoxybenzaldehyde, melting at 204-206 ° C., are obtained.
189,3 g (1,02 Mol) dieses Aldehyds werden in I Liter wasserfreiem Dimethylformaimd suspendiert und mit 350 g Kaliumcarbonat versetzt. Sodann werden innerhalb von 20 Minuten 145 ml (124 g, i,54 Mol) Dimethylsulfat zugetropft. Nach der Zugabe wird das Reaktionsgemisch auf einem Dampfbad 5 Minuten erhitzt. Sodann werden 70 ml Wasser zugegeben. Hierauf wird weitere 5 Minuten auf dem Dampfbad erhitzt. Das Gemisch wird sodann in Eiswasser gegossen. Der Niederschlag wird gewonnen und aus Essigsäure/Wasser (800/50 ml) kristallisiert. Eine zweite Ausbeute erhält man aus der Mutterlauge. Nach dem Trocknen erhält man 180 g (90 Prozent d.Th.) 2-Chlor-3,4-dimethoxybenzal-dehyd vom F. 69-70 CC. 189.3 g (1.02 mol) of this aldehyde are suspended in 1 liter of anhydrous dimethylformamide and mixed with 350 g of potassium carbonate. Then 145 ml (124 g, i, 54 mol) of dimethyl sulfate are added dropwise within 20 minutes. After the addition, the reaction mixture is heated on a steam bath for 5 minutes. Then 70 ml of water are added. This is followed by heating on the steam bath for a further 5 minutes. The mixture is then poured into ice water. The precipitate is collected and crystallized from acetic acid / water (800/50 ml). A second yield is obtained from the mother liquor. After drying, 180 g (90 percent of theory) of 2-chloro-3,4-dimethoxybenzaldehyde of melting point 69-70 CC are obtained.
180 g (0,9 Mol) Dimethoxybenzaldehyd werden in 500 ml warmer Essigsäure gelöst. Sodann werden 61g (0,8 Mol) Ammoniumacetat und anschliessend 160 ml Ni-tromethan zugesetzt. Das Reaktionsgemisch wird 3 Stunden heftig auf dem Dampfbad erhitzt. Anschliessend wird Wasser bis zum Trübungspunkt zugesetzt, wobei noch erwärmt wird. Nach dem Abkühlen der Lösung wird die Glaswand mit einem Glasstab gekratzt. ß-Nitrostyrol beginnt als Öl auszufallen und kristallisiert sodann. Anschliessend wird die Lösung gekühlt. Die gelben Kristalle werden gewonnen und in einem Vakuumtrockenschrank getrocknet. Man erhält 175 g (80 Prozent d.Th.) 2-Chlor-3,4-dimethoxy-ß-nitro-styrol vom F. 88-91 °C. 180 g (0.9 mol) of dimethoxybenzaldehyde are dissolved in 500 ml of warm acetic acid. Then 61 g (0.8 mol) of ammonium acetate and then 160 ml of Ni-tromethane are added. The reaction mixture is heated vigorously on the steam bath for 3 hours. Water is then added to the cloud point, with heating still taking place. After the solution has cooled, the glass wall is scratched with a glass rod. ß-nitrostyrene begins to precipitate as an oil and then crystallizes. The solution is then cooled. The yellow crystals are obtained and dried in a vacuum drying cabinet. 175 g (80 percent of theory) of 2-chloro-3,4-dimethoxy-β-nitro-styrene of melting point 88-91 ° C. are obtained.
80 g (0,33 Mol) des Nitrostyrols werden in 800 ml wasserfreiem Tetrahydrofuran gelöst. In einem 5 Liter fassenden Dreihalskolben, der getrocknet und mit Argon gespült worden ist, werden 260 ml (0,36 Mol) einer 3,7 m Lithiumaluminiumhydridlösung gegeben. Sodaim wird mit 500 ml wasserfreiem Diäthyläther verdünnt. Die Nitrostyrollösung wird sodann in einem feinen Strahl zugesetzt. Der Kolben wird in einem Eisbad gekühlt, so dass die Reaktionswärme für ein leichtes Rückflusskochen des Diäthyläthers sorgt. Nach der Zugabe wird das Reaktionsgemisch 1 Stunde unter Rückfluss erwärmt und anschliessend vorsichtig durch aufeinanderfolgende Zugabe von 36 ml Wasser, 36 ml einer lOprozentigen Natriumhydroxidlösung und 108 ml Wasser aufgearbeitet, wobei das Reaktionsgemisch in Eis gekühlt wird. 80 g (0.33 mol) of the nitrostyrene are dissolved in 800 ml of anhydrous tetrahydrofuran. 260 ml (0.36 mol) of a 3.7 m lithium aluminum hydride solution are placed in a 5 liter three-necked flask which has been dried and flushed with argon. Sodaim is diluted with 500 ml of anhydrous diethyl ether. The nitrostyrene solution is then added in a fine stream. The flask is cooled in an ice bath so that the heat of reaction allows the diethyl ether to reflux slightly. After the addition, the reaction mixture is heated under reflux for 1 hour and then carefully worked up by successively adding 36 ml of water, 36 ml of a 10% sodium hydroxide solution and 108 ml of water, the reaction mixture being cooled in ice.
Der Niederschlag wird gesammelt, gründlich mit Diäthyläther gewaschen und verworfen. Das Diäthyläther/ Tetrahydrofuran-Gemisch wird eingedampft. The precipitate is collected, washed thoroughly with diethyl ether and discarded. The diethyl ether / tetrahydrofuran mixture is evaporated.
Die vorstehende Umsetzung wird mit 83 g Nitrostyrol wiederholt. Die beiden Rohprodukte werden vereinigt und bei 0,5 Torr destilliert. Das Produkt mit einem Siedebereich The above reaction is repeated with 83 g of nitrostyrene. The two raw products are combined and distilled at 0.5 torr. The product with a boiling range
3 3rd
638 487 638 487
von 142-155 °C (80 g) erweist sich dünnschichtchromatogra-phisch als reines 2-(2-Chlor-3,4-dimethoxyphenyl)-äthyl-amin. from 142-155 ° C (80 g) turns out to be pure 2- (2-chloro-3,4-dimethoxyphenyl) ethylamine by thin layer chromatography.
25,7 g (0,12 Mol) Phenäthylamin werden in einem Ölbad auf 115 °C erwärmt. 14,4 g (0,12 Mol) Styroloxid werden zugesetzt. Das Reaktionsgemisch wird I Stunde erwärmt. 25.7 g (0.12 mol) of phenethylamine are heated to 115 ° C. in an oil bath. 14.4 g (0.12 mol) of styrene oxide are added. The reaction mixture is heated for 1 hour.
Nach dem Abkühlen auf etwa 30 °C wird ein 2:1-Gemisch aus Petroläther und Aceton zugegeben, um das Öl in Lösung zu bringen. 15 g (37 Prozent d.Th.) N-[(2-Hydroxy-2- After cooling to about 30 ° C, a 2: 1 mixture of petroleum ether and acetone is added to bring the oil into solution. 15 g (37 percent of theory) N - [(2-hydroxy-2-
phenyläthyl)]-N-[2-(2'-chlor-3',4'-dimethoxyphenyl)-äthyl]-amin vom F. 100-101 °C kristallisieren aus. phenylethyl)] - N- [2- (2'-chloro-3 ', 4'-dimethoxyphenyl) ethyl] amine, melting point 100-101 ° C, crystallize out.
Beispiel 3 Example 3
s 1,0 g 2-Chlor-3,4-dimethoxyphenäthylamin werden mit 0,70 g p-Methoxystyroloxid auf die vorstehend beschriebene Weise zu Hydroxyphenäthylamin vom F. 118,5-121 °C umgesetzt. s 1.0 g of 2-chloro-3,4-dimethoxyphenethylamine are reacted with 0.70 g of p-methoxystyrene oxide in the manner described above to give hydroxyphenethylamine with a melting point of 118.5-121 ° C.
Claims (3)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1401077A CH637383A5 (en) | 1978-01-01 | 1978-01-01 | Trisubstituted 1-phenyl-2,3,4,5-tetrahydro-1H-3-benzazepines, and their salts |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH638487A5 true CH638487A5 (en) | 1983-09-30 |
Family
ID=4397186
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH1401077A CH637383A5 (en) | 1978-01-01 | 1978-01-01 | Trisubstituted 1-phenyl-2,3,4,5-tetrahydro-1H-3-benzazepines, and their salts |
| CH680382A CH638487A5 (en) | 1978-01-01 | 1982-11-23 | Novel substituted di(phenylethyl)amines |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH1401077A CH637383A5 (en) | 1978-01-01 | 1978-01-01 | Trisubstituted 1-phenyl-2,3,4,5-tetrahydro-1H-3-benzazepines, and their salts |
Country Status (1)
| Country | Link |
|---|---|
| CH (2) | CH637383A5 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0125053A1 (en) * | 1983-04-28 | 1984-11-14 | Smithkline Beckman Corporation | Process for preparing secondary amines |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5068326A (en) * | 1989-04-03 | 1991-11-26 | Kung Hank F | Dopamine receptor ligands and imaging agents |
| EP2170343A1 (en) | 2007-05-31 | 2010-04-07 | Joseph Weinstock | Treatment of age-related macular degeneration |
-
1978
- 1978-01-01 CH CH1401077A patent/CH637383A5/en not_active IP Right Cessation
-
1982
- 1982-11-23 CH CH680382A patent/CH638487A5/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0125053A1 (en) * | 1983-04-28 | 1984-11-14 | Smithkline Beckman Corporation | Process for preparing secondary amines |
Also Published As
| Publication number | Publication date |
|---|---|
| CH637383A5 (en) | 1983-07-29 |
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