DE825416C - Process for the preparation of tertiary amines - Google Patents
Process for the preparation of tertiary aminesInfo
- Publication number
- DE825416C DE825416C DES2296A DES0002296A DE825416C DE 825416 C DE825416 C DE 825416C DE S2296 A DES2296 A DE S2296A DE S0002296 A DES0002296 A DE S0002296A DE 825416 C DE825416 C DE 825416C
- Authority
- DE
- Germany
- Prior art keywords
- hydrogen atom
- dioxacyclopentane
- halogen
- preparation
- tertiary amines
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D317/28—Radicals substituted by nitrogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von tertiären Aminen Die Erfindung betrifft ein Verfahren zur Herstellung von neuen tertiären Aminen, welche vom Dioxacyclopentan abgeleitet sind, der allgemeinen Formel: sowie deren quartären Salzen. In dieser Formel bedeutet R ein Wasserstoffatom oder einen Alkylrest, der gegebenenfalls durch eine Hydroxylgruppe oder durch einen Dialkylaminorest substituiert ist, R1 ein Wasserstoffatom oder einen Alkylrest, R2 und R3 identische oder verschiedene Alkylreste und n eine ganze Zahl.Process for the preparation of tertiary amines The invention relates to a process for the preparation of new tertiary amines which are derived from dioxacyclopentane, of the general formula: and their quaternary salts. In this formula, R denotes a hydrogen atom or an alkyl group which is optionally substituted by a hydroxyl group or by a dialkylamino group, R1 denotes a hydrogen atom or an alkyl group, R2 and R3 are identical or different alkyl groups and n is an integer.
Erfindungsgemäß werden die genannten tertiären Basen in ausgezeichneten Ausbeuten erhalten, wenn man die Halogenderivate der entsprechenden Dioxacyclopentane mit einem Dialkylamin behandelt. Die quartäred Salze werden entweder direkt erhalten, indem man dieselben Halogenderivate mit einem Trialkylamin kondensiert, oder vorzugsweise durch Zugabe eines Alkylhalogenids oder -sulfats zu den zuerst erhaltenen tertiären Basen.According to the present invention, the above-mentioned tertiary bases are excellent Yields obtained when the halogen derivatives of the corresponding dioxacyclopentanes treated with a dialkylamine. The quaternary salts are either obtained directly, by condensing the same halogen derivatives with a trialkylamine, or preferably by adding an alkyl halide or sulfate to the tertiary obtained first Bases.
Die oben angeführten Halogenderivate, welche zu der vorher beschriebenen Synthese dienen, werden ihrerseits erfindungsgemäß hergestellt, indem ein Halogenacetal vom Typ: (R, und n haben dieselbe Bedeutung, wie oben angeführt) mit einer Polyoxyverbindung vom Typ RQ CHOH-CH20H erhitzt wird. R, bedeutet ein Wasserstoffatom oder einen Alkylrest, der gegebenenfalls durch eine Hydroxylgruppe oder ein Halogenatom substituiert sein kann, das die weitere Substitution der Dialkyläminogruppe erlaubt.The halogen derivatives listed above, which are used for the synthesis described above, are in turn prepared according to the invention by using a halogen acetal of the type: (R, and n have the same meaning as given above) is heated with a polyoxy compound of the type RQ CHOH-CH20H. R 1 denotes a hydrogen atom or an alkyl radical which can optionally be substituted by a hydroxyl group or a halogen atom which allows further substitution of the dialkyl amino group.
Die erfindungsgemäß hergestellten quartären Ammoniumsalze haben bedeutende physiologische Eigenschaften, welche sie für die Verwendung in der Therapie geeignet machen.The quaternary ammonium salts prepared according to the invention have significant physiological properties which make them suitable for use in therapy do.
Die folgenden Beispiele zeigen die praktische Anwendung der Erfindung.The following examples demonstrate the practice of the invention.
Beispiel i Man erhitzt 31 g Äthylenglykol mit 99 g Bromacetal 4 Stunden im Ölbad auf i5o°, dann fraktioniert man die erhaltene Masse im Vakuum. Man erhält so 57 g 2-Brommethyl-i, 3-dioxacyclopentan, welches bei 79° unter 22 mm Hg-Druck siedet.Example i 31 g of ethylene glycol are heated with 99 g of bromoacetal for 4 hours in an oil bath to 150 °, then the mass obtained is fractionated in vacuo. You get so 57 g of 2-bromomethyl-i, 3-dioxacyclopentane, which at 79 ° under 22 mm Hg pressure boils.
25 g des vorstehenden Produkts werden im geschlossenen Rohr bei i5o° 15 Stunden mit 70 ccm einer benzolischen Lösung von Dimethylamin (33°/o) erhitzt. Nach dem Abkühlen entfernt man das Chlorhydrat des Dimethylamins, welches auskristallisiert ist, durch Filtration, entfernt den Überschuß an Dimethylamin und das Benzol durch Destillation und fraktioniert den Rückstand unter vermindertem Druck. Man erhält so 18 g 2-Dimethylaminomethyl-1, 3-dioxacyclopentan, welches bei 68° unter 20 mm übergeht. Durch Zugabe von Methyljodid erhält man das jodmethylat, welches aus Alkohol in bei 196° schmelzenden Blättchen kristallisiert. Beispiel 2 Man erhitzt eine Mischung von 23 g Glycerin und 49 g Bromacetal bei 15o° 4 Stunden, dann fraktioniert man die 3lasse unter vermindertem Druck. Man erhält so bei 152° unter 20 mm das 2-Brommethyl-4-hydroxymethyl-i, 3-dioxacyclopentan in einer Äusbeute von 75°/0, verunreinigt mit etwas 2-Brommethyl-5-hydroxy-i, 3-dioxacyclohexan.25 g of the above product are heated in a closed tube at 150 ° for 15 hours with 70 cc of a benzene solution of dimethylamine (33 ° / o). After cooling, the hydrochloride of the dimethylamine which has crystallized out is removed by filtration, the excess dimethylamine and the benzene are removed by distillation and the residue is fractionated under reduced pressure. This gives 18 g of 2-dimethylaminomethyl-1,3-dioxacyclopentane, which passes over at 68 ° below 20 mm. By adding methyl iodide, iodine methylate is obtained, which crystallizes from alcohol in flakes melting at 196 °. EXAMPLE 2 A mixture of 23 g of glycerol and 49 g of bromoacetal is heated at 150 ° for 4 hours, then the 3lasse is fractionated under reduced pressure. This gives 2-bromomethyl-4-hydroxymethyl-1,3-dioxacyclopentane at 152 ° below 20 mm in a yield of 75 ° / 0, contaminated with a little 2-bromomethyl-5-hydroxy-1,3-dioxacyclohexane.
3o g des vorstehenden Produkts werden im geschlossenen Rohr bei 13o° mit 40 ccm einer Lösung von Dimethylamin (33°/0) 12 Stunden erhitzt. Wenn man wie im vorhergehenden Beispiel aufarbeitet, erhält man bei 137° unter 27 mm das 2-Dimethylaminomethyl-4-hydroxymethyl-i, 3-dioxacyclopentan, das noch 2-Dimethylaminomethyl-5-hydroxy-i, 3-dioxacyclohexan enthält. Durch Zugabe von Methyljodid erhält man zwei jodmethylate, von denen das eine kristallisiert und bei 175° schmilzt, während das andere nicht kristallisiert.30 g of the above product are placed in a closed tube at 130 ° heated with 40 cc of a solution of dimethylamine (33 ° / 0) for 12 hours. If you like worked up in the previous example, 2-dimethylaminomethyl-4-hydroxymethyl-i is obtained at 137 ° below 27 mm, 3-dioxacyclopentane, which is also 2-dimethylaminomethyl-5-hydroxy-1,3-dioxacyclohexane contains. Adding methyl iodide gives two iodomethylates, one of which is one crystallizes and melts at 175 ° while the other does not crystallize.
Durch Einwirkung von Acetylchlorid auf die vorstehende Base erhält man deren Acetylderivat, das lx#i i0i unter 15 mm siedet. -Beispiel 3 Man erhitzt eine Mischung von 55 g a-Monochlorhydrin des Glycerins und 98 g Bromacetal auf dem Ölbad bei 13o° 4 Stunden. Wenn man die Masse, wie in den vorhergehenden Bespielen beschrieben, behandelt, erhält man in 75°, oiger Ausbeute das. 2-Brommethyl-4-chlormethy-l-r, 3-dioxacyclopentan, welches bei 112° unter 18 mm siedet und beim 48stündigen Erhitzen auf 17o° mit 6 Molekülen Dimethylamin in 3o°/oiger benzolischer Lösung das 2, 4-Di-(dimethylaminomethyl)-1, 3-dioxacyclopentan ergibt, das bei i2o° unter 20 mm siedet und dessen Dijodmethylat nach dem Umkristallisieren aus Alkohol bei i8o bis 18i° schmilzt.Obtained by the action of acetyl chloride on the above base their acetyl derivative, which boils lx # i i0i below 15 mm. - Example 3 Heating is carried out a mixture of 55 g of glycerol α-monochlorohydrin and 98 g of bromoacetal on the Oil bath at 130 ° for 4 hours. If you look at the crowd, as in the previous examples described, treated, is obtained in 75 °, oiger yield. 2-bromomethyl-4-chloromethyl-1-r, 3-dioxacyclopentane, which boils at 112 ° below 18 mm and when heated for 48 hours at 17o ° with 6 molecules of dimethylamine in 3o% benzene solution the 2,4-di- (dimethylaminomethyl) -1, 3-dioxacyclopentane results, which boils at i2o ° below 20 mm and its diiodomethylate after recrystallization from alcohol, it melts at between 180 and 18 °.
Beispiel 4 Man erhitzt 35 g Bromacetal mit 20 g Pentantriol-1, 2, 5 4 Stunden auf 130°. Nach dem Fraktionieren unter vermindertem Druck erhält man in 7o°/oiger Ausbeute das 2-Brommethy1-4-(3'-hydroxypropyl)-1, 3-dioxacyclopentan, welches bei der Behandlung mit einem Überschuß von Dimethylamin, wie in den vorhergehenden Beispielen beschrieben, das 2-Dimethylaminomethyl-4- (3'-hydroxypropyl) -1, 3-dioxacyclopentan ergibt, das bei 153° unter io mm siedet und dessen jodmethylat außerordentlich hygroskopisch ist.Example 4 35 g of bromoacetal are heated with 20 g of pentanetriol-1, 2, 5 4 hours at 130 °. Fractionation under reduced pressure gives 2-bromomethy1-4- (3'-hydroxypropyl) -1, 3-dioxacyclopentane in 70% yield, which upon treatment with an excess of dimethylamine, as in the preceding Examples described, the 2-dimethylaminomethyl-4- (3'-hydroxypropyl) -1, 3-dioxacyclopentane results, which boils at 153 ° below 10 mm and its iodomethylate is extremely hygroscopic is.
Claims (1)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR825416X | 1944-04-17 |
Publications (1)
Publication Number | Publication Date |
---|---|
DE825416C true DE825416C (en) | 1951-12-17 |
Family
ID=9282341
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DES2296A Expired DE825416C (en) | 1944-04-17 | 1950-03-17 | Process for the preparation of tertiary amines |
Country Status (1)
Country | Link |
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DE (1) | DE825416C (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1046627B (en) * | 1954-09-10 | 1958-12-18 | Thomae Gmbh Dr K | Process for the preparation of 2-aminomethyl-1,3-dioxolanes, their salts and quaternary ammonium compounds |
DE1122073B (en) * | 1957-11-12 | 1962-01-18 | Byk Gulden Lomberg Chem Fab | Process for the preparation of basic substituted 4- (o-tolyloxymethyl) -1,3-dioxolanes |
-
1950
- 1950-03-17 DE DES2296A patent/DE825416C/en not_active Expired
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1046627B (en) * | 1954-09-10 | 1958-12-18 | Thomae Gmbh Dr K | Process for the preparation of 2-aminomethyl-1,3-dioxolanes, their salts and quaternary ammonium compounds |
DE1122073B (en) * | 1957-11-12 | 1962-01-18 | Byk Gulden Lomberg Chem Fab | Process for the preparation of basic substituted 4- (o-tolyloxymethyl) -1,3-dioxolanes |
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