CH176831A - Process for the preparation of a cyclic amine. - Google Patents
Process for the preparation of a cyclic amine.Info
- Publication number
- CH176831A CH176831A CH176831DA CH176831A CH 176831 A CH176831 A CH 176831A CH 176831D A CH176831D A CH 176831DA CH 176831 A CH176831 A CH 176831A
- Authority
- CH
- Switzerland
- Prior art keywords
- carried out
- reduction
- cyclic amine
- acid
- preparation
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Hydrogenated Pyridines (AREA)
Description
Verfahren zur Herstellung eines cyclischem Amins. Es wurde gefunden, dass man zu einem cyclischen Amin gelangen kann, wenn man auf Cyclooctarion-thioisoxim (Lactam der 8- Aminooctaiithionsäure) ein Reduktionsmittel einwirken lässt.
Das auf diese Weise erhaltene Octa- methylenimin der Formel
EMI0001.0010
bildet ein 01 vom Kp?s <B>85-860.</B> Das Pikrat der Base schmilzt bei 148-1490.
Das neue Amin zeichnet sich durch seine physiologische Wirkung aus und soll thera peutische Verwertung finden.
Beispiel <I>1:</I> 5 Gewichtsteile Cyclooctanon-oxim wer den mit 10 Raumteilen Schwefelsäure (her gestellt durch Mischen von konzentrierter Säure und Wasser im Verhältnis 4:1) unter Umschütteln auf freier Flamme so lange erhitzt, bis heftige Reaktion eintritt. Nach dem Aufhören derselben wird das dunkel braune Gemisch erkalten gelassen und dann auf Eis gegossen. Nach dem Übersättigen mit Natronlauge extrahiert man erschöpfend mit Äther. Der Extrakt siedet bei 119-122 (0,7 mm) bezw. 164-166 (14 mm).
Der Schmelzpunkt des ganz erstarrenden Cyclo- octanon-isoxims (des Lactams der 8-Amino- octansäure) liegt nach dem Waschen mit Petroläther bei 72-73 .
Ein Gewichtsteil des Isoxims wird in 10 Raumteilen gylol gelöst und unter Rühren mit der Turbine mit 1,6 Gewichtsteilen Phos- phorpentasulfid versetzt. Das Gemisch erhitzt man allmählich auf 100 und lässt es 2 Stun den bei dieser Temperatur. Man fügt dann Natronlauge zu und erhitzt weiter bis alles in Lösung geht. Nach Abtrennung der Xy- lolschicht und Verdampfung des Lösungs mittels wird der Rückstand aus Benzin um kristallisiert.
Das erhaltene Cyclooctanon- thioisoxim (Lactam der 8-Aminooctanthion- säure schmilzt bei<B>890.</B> 8 Gewichtsteile Cyclooctanon-thioisoxim werden in 1500 Raumteilen absolutem Alko hol gelöst und dazu bei Siedetemperatur allmählich 300 Raumteile Eisessig und 55 Gewichtsteile Natrium eingetragen, wobei die Reaktion des Gemisches stets sauer bleibt. Den Alkohol \destilliert man mit Wasser dampf ab, übersättigt den Rückstand mit Natronlauge und zieht ihn mit Äther er schöpfend aus. Die ätherische Lösung schüt telt man mit Salzsäure.
Den salzsauren Aus zug macht man wieder alkalisch und nimmt das abgeschiedene Amin in Petrolätber auf. Durch Destillation im Vakuum wird das Octamethylenimin gereinigt.
Beispiel <I>2:</I> Man löst 50 gr Cy clooctanonthioisoxim in 1 Liter 55 o/oiger Schwefelsäure auf und elektrolysiert die Lösung unter Anwendung von Bleielektroden und Kühlung der Kathode. Als Anodenflüssigkeit dient 20 o;oige Schwe felsäure. Die Stromstärke beträgt 18 Ampi;re bei 5 Volt Spannung. Die Elektrolyse wird bei etwa 30 o während 5-6 Stunden durch geführt.
Hierauf wird die mit Alkali über sättigte Kathodenflüssigkeit mit Petroläther erschöpfend ausgezogen und nach Vertreiben des Lösungsmittels das Cyclooctamethyleni- min durch Destillation gereinigt.
Process for the preparation of a cyclic amine. It has been found that a cyclic amine can be obtained if a reducing agent is allowed to act on cyclooctarion-thioisoxime (lactam of 8-aminooctalithionic acid).
The octamethylene imine of the formula obtained in this way
EMI0001.0010
forms an 01 of the Kp? s <B> 85-860. </B> The picrate of the base melts at 148-1490.
The new amine is characterized by its physiological effect and should be used therapeutically.
Example <I> 1: </I> 5 parts by weight of cyclooctanone oxime are heated with 10 parts by volume of sulfuric acid (prepared by mixing concentrated acid and water in a ratio of 4: 1) with shaking over a free flame until a violent reaction occurs . After this has stopped, the dark brown mixture is allowed to cool and then poured onto ice. After supersaturation with sodium hydroxide solution, extraction is carried out exhaustively with ether. The extract boils at 119-122 (0.7 mm) respectively. 164-166 (14 mm).
The melting point of the completely solidifying cyclooctanone isoxime (the lactam of 8-amino octanoic acid) is 72-73 after washing with petroleum ether.
One part by weight of the isoxime is dissolved in 10 parts by volume of gylene and 1.6 parts by weight of phosphorus pentasulfide are added while stirring with the turbine. The mixture is gradually heated to 100 and left for 2 hours at this temperature. Sodium hydroxide solution is then added and heating continues until everything goes into solution. After the xylene layer has been separated off and the solvent has evaporated, the residue is recrystallized from gasoline.
The resulting cyclooctanone thioisoxime (lactam of 8-aminooctanthionic acid melts at 890. 8 parts by weight of cyclooctanone thioisoxime are dissolved in 1500 parts by volume of absolute alcohol and 300 parts by volume of glacial acetic acid and 55 parts by weight of sodium are gradually added at the boiling point The reaction of the mixture always remains acidic. The alcohol is distilled off with steam, the residue is supersaturated with sodium hydroxide solution and it is extracted with ether. The ethereal solution is shaken with hydrochloric acid.
The hydrochloric acid extract is made alkaline again and the separated amine is taken up in petroleum ether. The octamethyleneimine is purified by distillation in vacuo.
Example <I> 2: </I> 50 g of cyclooctanonthioisoxime are dissolved in 1 liter of 55% sulfuric acid and the solution is electrolyzed using lead electrodes and cooling the cathode. 20% sulfuric acid is used as the anolyte. The current is 18 amps at 5 volts. The electrolysis is carried out at about 30 o for 5-6 hours.
The catholyte, saturated with alkali, is then exhausted with petroleum ether and, after the solvent has been driven off, the cyclooctamethyleneimine is purified by distillation.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH172873T | 1933-08-22 | ||
| CH176831T | 1933-08-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH176831A true CH176831A (en) | 1935-04-30 |
Family
ID=25719291
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH176831D CH176831A (en) | 1933-08-22 | 1933-08-22 | Process for the preparation of a cyclic amine. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH176831A (en) |
-
1933
- 1933-08-22 CH CH176831D patent/CH176831A/en unknown
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