DE1081463B - Process for the production of polysubstituted acetic acid morpholides - Google Patents
Process for the production of polysubstituted acetic acid morpholidesInfo
- Publication number
- DE1081463B DE1081463B DER24144A DER0024144A DE1081463B DE 1081463 B DE1081463 B DE 1081463B DE R24144 A DER24144 A DE R24144A DE R0024144 A DER0024144 A DE R0024144A DE 1081463 B DE1081463 B DE 1081463B
- Authority
- DE
- Germany
- Prior art keywords
- acetic acid
- phenyl
- polysubstituted
- production
- acetoxy
- 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.)
- Pending
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von mehrfach substituierten Essigsäuremorpholiden Es wurde gefunden, daß man Essigsäuremorpholide der Formel worin R einen Phenyl- oder Monooxy- oder Dioxyphenylrest und R1H oder einen niederen Alkylrest bedeutet, herstellen kann, indem man ß,ß'-Diacetoxydi@alkyl-acetylamine der Formel worin R1 die oben angegebene Beadeutung hat und R2 einen Phenyl- oderAcetoxy-oder Diacetoxyphenylrest bedeutet, in Eisessig, dem etwa eine den Acetoxygruppen äquivalente Menge an Wasser zugesetzt ist, erhitzt. Beispielsweise verwendet man auf 1 Mol 1-Phenyl-l-acetoxy-2-acetoxyäthylacetylami.no-propan 2 Mol Wasser. Beim Kochen unter Rückfluß, z. B. bei 120° C für die Dauer von 10 Stunden, oder im Druckgefäß bei 160° C, im Verlauf von 5 Stunden, bilden sich d@i@e Essigsäuremorpholide, wie Essigsäure-(2-phenyl-3-methyl)-mo,rpholid, - in sehr guter Ausbeute. Gleichzeitig werden bei Verwendung von am Phenylkern substituierten Ausgangsprodukten die Acetoxygruppen ebenfalls verseift, wobei für jeder der am Phenylring vorliegendenAcotoxygruppen ein weiteres Mol Wasser dem Eisessig zuzusetzen ist.Process for the preparation of polysubstituted acetic acid morpholides It has been found that acetic acid morpholides of the formula in which R is a phenyl or monooxy or dioxyphenyl radical and R1 is H or a lower alkyl radical, can be prepared by β, β'-diacetoxydi @ alkyl-acetylamines of the formula where R1 has the meaning given above and R2 denotes a phenyl or acetoxy or diacetoxyphenyl radical, heated in glacial acetic acid to which an amount of water equivalent to about the acetoxy groups has been added. For example, 2 moles of water are used for 1 mole of 1-phenyl-1-acetoxy-2-acetoxyäthylacetylami.no-propane. When refluxing e.g. B. at 120 ° C for a period of 10 hours, or in a pressure vessel at 160 ° C for 5 hours, d @ i @ e acetic acid morpholides, such as acetic acid (2-phenyl-3-methyl) -mo , rpholid, - in very good yield. At the same time, when starting materials substituted on the phenyl nucleus are used, the acetoxy groups are also saponified, an additional mole of water being added to the glacial acetic acid for each of the acetoxy groups present on the phenyl ring.
Eigenartigerweise lassen sich die beanspruchten Essigsäuremorpholiide aus ß,ß'-Diacetoxy-äthyl-alkylaminen der Formel II nur nach dem erfindungsgemäßen Herstellungsverfahren gewinnen. Setzt man z. B. an Stelle des Eisessigs EssigsäuTeanhydri-d ein, so erhält man die Ausgangsprodukte zurück. Andererseits bilden sich bei Verwendung von 70°/miger Schwefelsäure am Stickstoff unsubstituierte Morpholinverbindungen; während wäßrige Salzsäure lediglich zu Verseifungsprodukten führt.Strangely enough, the claimed acetic acid morpholids can be from ß, ß'-diacetoxy-ethyl-alkylamines of the formula II only according to the invention Win manufacturing process. If you put z. B. instead of glacial acetic acid, acetic acid anhydride one gets back the starting products. On the other hand, form when used morpholine compounds unsubstituted by 70% sulfuric acid on nitrogen; while aqueous hydrochloric acid only leads to saponification products.
Die erhitzte Reaktionslösung dampft man im Wasserstrahlvakuurn ein und destilliert Iden Rückstand an der Ölpumpe. Die erfindungsgemäßen Verbindungen gehen in sehr guter Ausbeute als leichtgelbliche, viskose Öle über. Mit von Bedeutung für die überaus große Wirtschaftlichkeit des beanspruchten Verfahrens ist die leichte Zugänglichkeit der Ausgangssubstanzen gemäß Formel II, welche sich in einem Einstufenverfahren herstellen lassen: 1-R-Propanol-(1)-on-2 wird mit Aminoalkoholen, wie 1-Amino-äthanol-(2) oder 1-Amino-propanol-(2), in Essigsäureanhydrid gelöst und in Gegenwart von Hydrierungskata.lysatoren, wie P@d-Kohle oder Raneynickel, hydriert, wobei auch gleichzeitig Veresiterung und Acylierung stattfinden. Man trennt .den Katalysator ab, dunstet das EssigsiLureanhydri,d an der Wasserstrahlpumpe ab und destilliert gegebenenfalls den Rückstand in gutem Ölpumpenvakuum. Die Verbindungen nach FormelII gehen -als gelbe, sehr viskose Öle über (z. B. 1-Phenyl-1-acetoxy-2-acetoxyäthylacetylamino-propan beim Kp.o,7 188° C).The heated reaction solution is evaporated in a water jet vacuum and distilled the residue on the oil pump. The compounds according to the invention pass over in very good yield as pale yellowish, viscous oils. With of importance for the extremely high economic efficiency of the claimed process is the easy one Accessibility of the starting substances according to formula II, which are in a one-step process can be produced: 1-R-propanol- (1) -one-2 is mixed with amino alcohols, such as 1-amino-ethanol- (2) or 1-amino-propanol- (2), dissolved in acetic anhydride and in the presence of hydrogenation catalysts, like P @ d-coal or Raney nickel, hydrogenated, whereby also at the same time Veresiterung and Acylation take place. The catalyst is separated off, the acetic anhydride evaporates, i on the water jet pump and, if necessary, distilled the residue in good condition Oil pump vacuum. The compounds according to formula II go as yellow, very viscous oils about (e.g. 1-phenyl-1-acetoxy-2-acetoxyäthylacetylamino-propane at bp 7,188 ° C).
Die erfindungsgemäßen Verbindungen, wie Essigsäure-(2-phenyl-3,miethyl)-morpholid, stellen wertvolle, z. B. kreislaufwirksame Arzneimittel bzw. Zwischenprodukte in der Arzneimittelsynthesedar. Beispiel 1 32,5g 1-Phenyl-l-acetoxy-2-acetoxyäthylacetyiamino-propan werden in 200 ml Eisessig gelöst, 5,4 ml Wasser zugefügt und für die Dauer von 5 Stunden auf 160° C erhitzt. Anschließend vdeht man den Eisessig an der Wasserstrahlpumpe ab und destilliert den Rückstand bei Kp.o,a 138° C. Das Essigsäure-(2-phenyl-3-methyl)-morphol.i(d geht als schwachgebliches Öl über. Ausbeute: 91 % der Theorie.The compounds according to the invention, such as acetic acid (2-phenyl-3, methyl) morpholide, are valuable, for. B. circulatory active drugs or intermediates in the drug synthesis. Example 1 32.5 g of 1-phenyl-1-acetoxy-2-acetoxyethylacetyiamino-propane are dissolved in 200 ml of glacial acetic acid, 5.4 ml of water are added and the mixture is heated to 160 ° C. for 5 hours. The glacial acetic acid is then removed using a water jet pump and the residue is distilled at a boiling point of 138 ° C. The acetic acid (2-phenyl-3-methyl) morphol.i (d passes over as a weak oil. Yield: 91 % of theory.
Beispiel 2 38g 1-p-Acetoxyphenyl-l-acetoxy-2-acetoxyäthylacetylamino-propan werden in 200 ml Eisessig gelöst, 7,2 ml Wasser hinzugefügt und für die Dauer von 10 Stunden auf 130° C erhitzt. Anschließend zieht man, nach einer weiteren Zugabe von 25 ml Wasser, das Lösungsmittel im Wasserstrahlvakuum ab und destilliert,den Rückstand im guten Ölpumpenvakuum.Example 2 38 g of 1-p-acetoxyphenyl-1-acetoxy-2-acetoxyethylacetylamino-propane are dissolved in 200 ml of glacial acetic acid, 7.2 ml of water are added and for a period of Heated to 130 ° C for 10 hours. Then pulls man, after a further addition of 25 ml of water, and the solvent in a water jet vacuum distilled, the residue in a good oil pump vacuum.
Essigsäure-(2-p--oxyphenyl-3'-mrefihyl) -morpholid geht beim KP-0,4 162° C als gelbliches, viskoses Öl über. Ausbeute: 870/9 der Theorie.Acetic acid- (2-p-oxyphenyl-3'-mrefihyl) -morpholide works with KP-0,4 162 ° C as a yellowish, viscous oil over. Yield: 870/9 of theory.
Die Herstellung der Ausgangssubstanzen wird nicht beansprucht.The production of the starting substances is not claimed.
Claims (1)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DER24144A DE1081463B (en) | 1958-10-03 | 1958-10-03 | Process for the production of polysubstituted acetic acid morpholides |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DER24144A DE1081463B (en) | 1958-10-03 | 1958-10-03 | Process for the production of polysubstituted acetic acid morpholides |
Publications (1)
Publication Number | Publication Date |
---|---|
DE1081463B true DE1081463B (en) | 1960-05-12 |
Family
ID=7401593
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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DER24144A Pending DE1081463B (en) | 1958-10-03 | 1958-10-03 | Process for the production of polysubstituted acetic acid morpholides |
Country Status (1)
Country | Link |
---|---|
DE (1) | DE1081463B (en) |
-
1958
- 1958-10-03 DE DER24144A patent/DE1081463B/en active Pending
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