DE896810C - Process for the preparation of tertiary alkynamines - Google Patents

Description

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.

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.

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.

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 °.

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.

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.

The parts given in the examples below are parts by weight.

-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.

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.

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)

PATENT CLAIM: Process for the production of tertiary alkynamines, characterized in that halogen derivatives of alkynes with at least one for Triple bond a halogen atom in the molecule reacted with secondary amines will.