DE946708C - Process for the preparation of ª ‰ -oxypyrrolidines - Google Patents

Description

Process for the production of ß-Oxypyrrolidi.nen It has been found that you get ß-Oxypyrrohdine, if you ß-Halogenäthyläthylenoxde with ammonia or primary amines.

In addition to ammonia, the primary saturated substances are suitable as starting materials or unsaturated aliphatic, cycloaliphatic, araliphatic or aromatic Mono- or diamines, such as methylamine, ethylamine, butylamine, dodecylamine, stearylamine, Oleylamine, cyclohexylamine, benzylamine, and aniline, as well as ethylene, hexylene or p-phenylenediamine or benzidine. You can also look at the carbon atoms more Groups, e.g. B. hydroxyl, alkoxy or ester groups wear. Such connections are z. B. monoethanolamine, monopropanolamine or glycollester. Diamines can be reacted on only one amino group or on both.

As ß-Halogenäthyläthylenoxyde are preferably the ß-chlorine and the ß-Bromäthyläthylenoxid used.

The reaction is expediently carried out in the presence of hydrogen halide binders Agents such as alkali or alkaline earth hydroxides or ammonium carbonates; or an excess of the amine. In particular, it is useful when using ammonia huge Excess of the calculated amount, e.g. B. to use 6 to 8 times the amount; whereby it is at the same time beneficial in the present. of ammonium carbonate to work. If you only work with a small excess of ammonia or without the addition of ammonium carbonate, so the yields are worse.

The reaction temperature chosen is ammonia or the low molecular weight one Amines advantageously the room temperature, while higher molecular weight amines are heated, z. B. at ioo to 18o °, implemented.

Solvents are generally not required, but one can optionally also inert diluents, e.g. B. chlorobenzene or dichlorobenzene, to add.

The ß-oxypyrrolidines, if appropriate, can be derived from the reaction mixtures after the addition of alkali or alkaline earth hydroxides, in a simple manner, for. B. by Distillation, win, taking as by-products when using primary Small quantities of diamines also include the corresponding N, N'-bis (ß-oxypyrrolidino) compounds can be obtained. 'The ß-oxypyrrolidines are easily accessible according to the invention valuable intermediates.

The parts given in the examples are parts by weight.

Example i 500 parts of 25% ammonia are mixed with 500 parts Ammonium carbonate in 100 parts of water and contributes 533 parts at 10 ° with stirring ß-Chloräthyläthylenoxid slowly a. When the addition is complete, the mixture is stirred for a further z to 3 hours at 15 ° and then about 55oo parts of water and ammonia are distilled away. The solution remaining in the still becomes 50% aqueous with 35o parts Potassium hydroxide solution is added and the precipitated potassium chloride is separated off. The filtrate will fractionally distilled under reduced pressure. 24o parts of β-oxypyrrolidine are obtained from Kp.l. io8 to iio °.

EXAMPLE 2 212 parts of β-chloroethylethylene oxide are slowly run in to 292 parts of n-butylamine while boiling on a reflux condenser and with stirring, and the mixture is then stirred for a further 2 hours at 100 °. 150 parts of 50% aqueous sodium hydroxide solution are added and the mixture is fractionally distilled under reduced pressure. Salt that drops out is separated from time to time. 220 parts of n-butyl ß-oxypyrrolidine with a boiling point of 115 to 1180 are obtained. EXAMPLE 3 106 parts of ß-chloroethylethylene oxide are introduced into 266 parts of technical stearylamine at 150 ° with stirring. Then it is heated. to 16o to 18o ° and stir for a further 2 hours. After adding 80 parts of aqueous sodium hydroxide solution and separating off the sodium chloride, the residue is distilled in a high vacuum. 28o parts of N-stearyl .beta.-oxypyrrolidine of bp 220.degree. To 260.degree. Are obtained. EXAMPLE 4 In a mixture of 232 parts of hexamethylenediamine and 225 parts of 50% aqueous potassium hydroxide solution, 213 parts of .beta.-chloroethylethylene oxide are added at 100.degree The mixture is stirred for a further 2 hours at 100 to 110 °. After cooling, alcohol is added, the precipitated salt is filtered off with suction and the fractionated distillation is carried out under reduced pressure. Aminohexyl) -p-oxypyrrolidine. The follow-up consists of 55 parts of i, 6-bis- (ß-oxypyrrolidino) -hexane with a boiling point of 1225-235 '.

Example s Märt has 61 parts of monoethanolamine and 112 parts So% aqueous potassium hydroxide solution with stirring and boiling under reflux cooling 10 6 parts ß-Chloräthyläthylenoxid run slowly, the temperature rises to 115 °. The mixture is stirred for a further 2 hours at 100 to 115 °. After cooling, the salt is sucked off and the filtrate is distilled. 60 parts of N- (2-oxyethyl) ß-oxypyrrolidine are obtained from Kp. "165 to 168 °.

EXAMPLE 6 212 parts of β-chloroethylethylene oxide are run in to 396 parts of cyclohexylamine at 14 ° to 150 ° with stirring and reflux, and the mixture is stirred at this temperature for a further 2 hours. 225 parts of 50% aqueous potassium hydroxide solution are added and the precipitated salt is filtered off with suction. The filtrate is fractionally distilled under reduced pressure. After an initial run of excess cyclohexylamine, 24o parts of N-cyclohexyl-β-oxypyrrolidine with a boiling point of 17 150 to 15 ° are obtained.

Claims (1)

PATENT CLAIM: Process for the preparation of ß-oxypyrrolidines, characterized in that ß-haloethylethylene oxides are reacted with ammonia or primary amines.