DE896810C - Process for the preparation of tertiary alkynamines - Google Patents
Process for the preparation of tertiary alkynaminesInfo
- Publication number
- DE896810C DE896810C DEB16873A DEB0016873A DE896810C DE 896810 C DE896810 C DE 896810C DE B16873 A DEB16873 A DE B16873A DE B0016873 A DEB0016873 A DE B0016873A DE 896810 C DE896810 C DE 896810C
- Authority
- DE
- Germany
- Prior art keywords
- tertiary
- alkynamines
- parts
- preparation
- stirring
- 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 3
- 238000002360 preparation method Methods 0.000 title description 2
- 150000003335 secondary amines Chemical class 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 150000001345 alkine derivatives Chemical class 0.000 claims description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000012433 hydrogen halide Substances 0.000 description 3
- 229910000039 hydrogen halide Inorganic materials 0.000 description 3
- -1 Alkyne amines Chemical group 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- UBBYIASQBXHRRC-UHFFFAOYSA-N hypochlorous acid piperidine Chemical compound OCl.C1CCNCC1 UBBYIASQBXHRRC-UHFFFAOYSA-N 0.000 description 1
- LPFHMAKISUGBIO-UHFFFAOYSA-N n-ethylethanamine;hypochlorous acid Chemical compound ClO.CCNCC LPFHMAKISUGBIO-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/08—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung tertiärer Alkinamine Es ist bekannt, tertiäre Alkinamine durch Umsetzung sekundärer Amine mit Formaldehyd und Acetylen unter Druck oder von 2, 3-Dibrompropen-(1) mit sekundären Aminen unter nachfolgender Halogenwasserstoffabspaltung mit Natriumamid in flüssigem Ammoniak herzustellen.Process for the preparation of tertiary alkynamines It is known, tertiary Alkyne amines by reacting secondary amines with formaldehyde and acetylene under pressure or of 2,3-dibromopropene- (1) with secondary amines with subsequent elimination of hydrogen halide with sodium amide in liquid ammonia.
Es wurde nun gefunden, daß man in technisch einfacher Weise zu mono- bzw. bis-tertiären Alkinaminen gelangt, wenn man Halogenderivate von Alkinen mit mindestens einem zur Dreifachbindung a-ständigen Halogenatom im Molekül mit sekundären Aminen umsetzt.It has now been found that it is technically simple to mono- or bis-tertiary alkynamines, if you use halogen derivatives of alkynes at least one halogen atom in the a-triple bond in the molecule with secondary Converts amines.
Geeignete derartige Halogenderivate sind beispielsweise Alkinhalogenide der allgemeinen Formeln Hal-CHR-C= C-CHR-Hal und Hal-CHR-C--C-R, wobei R Wasserstoff bzw. ein Alkyl-, Aryl-, Aralkyl-oder Cycloalkylrest sein kann. Als sekundäre Amine kommen z. B. Dimethylamin, Diäthylamin, Methyläthyjamin, Methylanilin, Pyrrolidin, Piperidin, Morpholin, Hexamethylenimin u. dgl. in Betracht.Suitable halogen derivatives of this type are, for example, alkyne halides of the general formulas Hal-CHR-C = C-CHR-Hal and Hal-CHR-C - C-R, where R is hydrogen or an alkyl, aryl, aralkyl or cycloalkyl radical. As secondary amines come z. B. dimethylamine, diethylamine, methylethylamine, methylaniline, pyrrolidine, Piperidine, morpholine, hexamethyleneimine and the like.
Die Umsetzung kann ohne und mit Verdünnungsmitteln, wie Benzol, Xylol, Alkohole u. dgl., bei Zimmertemperatur oder mäßig erhöhten Temperaturen, zweckmäßig zwischen 5o bis 15o°, erfolgen.The reaction can be carried out with and without diluents such as benzene, xylene, Alcohols and the like, at room temperature or at moderately elevated temperatures, are expedient between 5o and 15o °.
Zur Bindung des bei der Reaktion frei werdenden Halogenwasserstoffs kann man so vorgehen, daß man auf ein umzusetzendes Halogenatom mindestens 2 Moleküle sekundäres Amin verwendet, oder man setzt andere halogenwasserstoffbindende Stoffe, wie Alkali- bzw. Erdalkalicarbonate, zu. Bei Anwendung eines Überschusses an sekundären Aminen gestaltet sich die Aufarbeitung der Reaktionsprodukte häufig besonders einfach.For binding the hydrogen halide released during the reaction one can proceed in such a way that there are at least 2 molecules per halogen atom to be converted secondary amine is used, or other substances that bind hydrogen halide are used, such as alkali or alkaline earth carbonates, too. When applying an excess of secondary In amines, the work-up of the reaction products is often particularly simple.
Die Isolierung der tertiären Alkinamine erfolgt in der üblichen Weise durch Destillation bzw. Kristallisation, gegebenenfalls nach Zugabe von Alkali- bzw. Erdalkalihydroxyden und Abdestillieren der als säurebindendes Mittel im ÜberschuB verwendeten sekundären Amine. Man erhält die tertiären Alkinamine in der Regel in hoher Ausbeute.The tertiary alkynamines are isolated in the usual way by distillation or crystallization, if necessary after the addition of alkali respectively. Alkaline earth hydroxides and distilling off as acid-binding Secondary amines used in excess. The tertiary alkynamines are obtained usually in high yield.
Die in den nachstehenden Beispielen angegebenen Teile sind Gewichtsteile.The parts given in the examples below are parts by weight.
-Beispiel-1 Zu ¢3o Teilen Pyrrolidin werden bei 2o° unter Rühren 123 Teile 1, 4-Dichlorbutin-(2) innerhalb von 1 Stunde zugetropft. Nach 2stündigem Nachrühren wird die obere- Schicht abgetrennt und fraktioniert destilliert. Bei 116 bis 116,5° unter einem Druck von 2,5 mm Hg geht das 1, q.-Bis-pyrrolidyl-butin-(2) in einer Ausbeute von g1 °/o über.-Example-1 To 300 parts of pyrrolidine are added 123 at 20 ° with stirring Parts 1,4-dichlorobutyn- (2) were added dropwise over the course of 1 hour. After stirring for 2 hours the upper layer is separated and fractionally distilled. At 116 to 116.5 ° under a pressure of 2.5 mm Hg the 1, q.-bis-pyrrolidyl-butyne- (2) goes in one Yield of g1% over.
Beispiel 2 Zu 146 Teilen Diäthylamin werden bei 6o° unter Rühren innerhalb 1 Stunde 62 Teile 1, 4.-Dichlorbutin-(2) zugegeben. Nach 1stündigem Nachrühren und Abkühlen wird von ausgeschiedenem Diäthylaminchlorhydrat abfiltriert und das Filtrat fraktioniert destilliert. Bei 131 bis 13q.° unter einem Druck von 6 mm Hg gehen 5o Teile 1, 4.-Bis-(diäthylamino)-butin-(2) über.EXAMPLE 2 146 parts of diethylamine are added at 60 ° with stirring within 1 hour 62 parts of 1,4-dichlorobutyne- (2) were added. After stirring for 1 hour and Cooling is filtered off from the precipitated diethylamine chlorohydrate and the filtrate fractionally distilled. At 131 to 13q. °, walk under a pressure of 6 mm Hg 5o parts 1, 4.-bis- (diethylamino) -butyne- (2) over.
Beispiel 3 In r8o Teile Piperidin werden bei 6o bis 7o° unter Rühren 62 Teile 1, 4-Dichlorbutin-(2) eingetragen. Nach 1stündigem Nachrühren und Abtrennen von ausgeschiedenem Piperidinchlorhydrat werden bei der Destillation bei 16o bis 161° unter einem Druck von 5 mm Hg 7o Teile 1, 4-Bis-piperidyl-butin-(2) erhalten. Die Aufarbeitung kann auch durch Alkalisieren des Reaktionsgemisches, Abtrennen der öligen Schicht und Destillation der letzteren erfolgen.Example 3 80 parts of piperidine are added at 6o to 7o ° with stirring 62 parts 1, 4-dichlorobutyn- (2) entered. After stirring and separating for 1 hour of excreted piperidine chlorohydrate are distilled at 16o to 161 ° obtained under a pressure of 5 mm Hg 70 parts 1, 4-bis-piperidyl-butyne- (2). Working up can also be carried out by making the reaction mixture alkaline and separating the oily layer and distillation of the latter take place.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB16873A DE896810C (en) | 1951-09-23 | 1951-09-23 | Process for the preparation of tertiary alkynamines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB16873A DE896810C (en) | 1951-09-23 | 1951-09-23 | Process for the preparation of tertiary alkynamines |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE896810C true DE896810C (en) | 1953-11-16 |
Family
ID=6959086
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEB16873A Expired DE896810C (en) | 1951-09-23 | 1951-09-23 | Process for the preparation of tertiary alkynamines |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE896810C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2830049A (en) * | 1956-05-28 | 1958-04-08 | Lakeside Lab Inc | Acetylenic tetrahydroisoquinoline derivatives |
| DE1206426B (en) * | 1960-02-29 | 1965-12-09 | Lilly Co Eli | Process for the preparation of an alkynamine |
-
1951
- 1951-09-23 DE DEB16873A patent/DE896810C/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2830049A (en) * | 1956-05-28 | 1958-04-08 | Lakeside Lab Inc | Acetylenic tetrahydroisoquinoline derivatives |
| DE1206426B (en) * | 1960-02-29 | 1965-12-09 | Lilly Co Eli | Process for the preparation of an alkynamine |
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