DE1164411B - Process for the preparation of 5-methylene-oxazolidonen- (2) - Google Patents

Description

Process for the preparation of 5-methylene-oxazolidone- (2) It has been found that 5-methylene-oxazolidone- (2) of the general formula obtained when acetylenamines of the general formula with carbon dioxide under elevated pressure and at elevated temperature in the presence of copper salts. In the formulas, R and R 'denote hydrogen atoms or aliphatic, cycloaliphatic, araliphatic or aromatic radicals or together members of a cycloaliphatic ring and R "denotes a hydrogen atom or an aliphatic or araliphatic radical which is optionally substituted by indifferent groups.

The formula can be expressed as follows: As acetylenamines, according to known methods, for. B. by reacting acetylene chlorides with primary, aliphatic or araliphatic amines, which can optionally be substituted by inert groups such as hydroxyl, alkoxy, acetal or dialkylamino groups, or ammonia, easily accessible acetyleneamines are used, eg. B. 3-methyl-3-n-butylamino-butyne- (l), 3-methyl-3-methylamino-butyne- (1), 3-methyl-3-n-butylamino-hexyne- (l), 3,5- Dimethyl-3-isopropylamino - hexyne - (1), 3 - n - butyl - 3 - benzylaminoheptine- (l), 3-ethyl-3-ethylamino-pentyne- (l), 3-n-butyl - 3 -methylamino - heptyne - (1), 1 - ethynyl -1- ethylamino-cyclohexane, 1-ethynyl- 1 -methylaminocyclopentane, l-ethynyl-l-benzylamino-cyclooctane, 3-phenyl-3-methylamino-butyne - (1), 3 - Cyclohexyl - 3-isopropylamino-butyne- (l), 1-ethynyl- 1 -n-butylaminocyclohexane, 3-isopropylamino-butyne- (1), 3-methyl-3-isopropylamino-butyne - (1), 3-benzylamino - propyne- (l), l-ethynyl-l-aminocyclohexane. In the case of weakly basic acetyleneamines, it is often advantageous to add tertiary amines, such as trimethylamine, triethylamine or tributylamine, in amounts of 1/2 to 20 percent by weight, based on the acetylenamine.

This can increase the yield of oxazolidone.

Carbon dioxide is injected under pressure. A print from 3 to 50 atü is usually sufficient.

But it can also be used at higher pressures.

The copper salts used as catalysts are in amounts of 0.05 to 5 percent by weight, based on acetyleneamines, added. One can do different Use copper salts, e.g. B. copper (I) chloride, copper (II) formate, copper (II) acetate or other copper (II) salts of organic acids, copper (II) sulfate or with copper ions loaded ion exchangers.

The reaction runs even at a slightly elevated temperature, e.g. B. 30 up to 40 "C. In general, however, a higher temperature between 40 and 1500C, especially 50 to 85 "C, preferred.

The use of a solvent such as tetrahydrofuran, dioxane or benzene, is recommended especially if the used Acetylenamines or the resulting substances are crystalline compounds.

The reaction can e.g. B. be carried out in an autoclave by one to the acetylenamine in the presence of copper salts carbon dioxide with 20 at to presses to saturation and then heats up to 50 to 85 "C for a few hours.

The reaction can also be carried out continuously in a pressure tube carry out according to the so-called trickle method or according to the so-called sump method.

The end products are generally isolated by distillation or crystallization.

The new compounds can be used to produce copolymers use as fungicides, rust inhibitors and intermediates.

The parts given in the examples are parts by weight.

Example 1 150 parts of 3-methyl-3-n-butylamino-butyne- (1), 300 parts Tetrahydrofuran, 15 parts of triethylamine and parts of copper (I) chloride are in the autoclave stirred under a carbon dioxide pressure of 20 at for 4 hours at room temperature, then is heated to 70 ° C. within 4 hours and kept at this temperature for 2 hours and then heated again to 800 C for 4 hours. The autoclave discharge results after filtration and distillation 128 parts of 3 -n-butyl-5-methylene-4,4-dimethyl-oxazolidone- (2) of Kr.1.5 102 "C, n2D = 1.4647.

If instead of 150 parts of 3-methyl-3-n-butylamine-butyne- (1) 100 parts of 3-benzylaminopropyne- (1), 64 parts of 3-benzyl-5-methylene-oxazolidone- (2) are obtained of m.p. 37 ° C. When using 100 parts of 1-ethynyl-1-amino-cyclohexane is obtained 68 parts of 5-methylene-4,4spirohexane-oxazolidone- (2) with a melting point of 112 "C.

Example 2 100 parts of 1-ethynyl-l-ethylamino-cyclohexane are in Dissolved 100 parts of benzene and, after adding 4 parts of copper (I) chloride, in the autoclave Stirred for 6 hours at room temperature at a carbon dioxide pressure of 20 atm, then the autoclave is heated to 95 ° C. within 6 hours and at kept this temperature.

The distillation of the discharge gives 85 parts of 3-ethyl-5-methylene - 4,4- spirohexane - oxazolidone - (2) of bp 110 ° C.

Is used instead of 100 parts of 1-ethynyl-1-ethylaminocyclohexane 100 parts of 1-ethynyl-I-n-butylamino-cyclohexane, 92 parts of 3-n-butyl-5-methylene-4,4-spirohexane-oxazolidone- (2) are obtained of Kr 0.15 1300C.

Example 3 250 parts of 3-isopropylamino-butyne- (1) and 3 parts of copper (I) chloride are in the autoclave at a carbon dioxide pressure of 50 at 8 hours at room temperature stirred, then heated to 75 ° C within 12 hours and a further 12 hours kept this temperature. When the autoclave is distilled, one obtains 210 parts of 3-isopropyl-5-methylene-4-methyl-oxazolidone- (2) with a boiling point of 67 "C, n2Ds = 1.4635.

Example 4 100 parts of 3 - methyl - 3 - isopropylamino - butyne - (1) are dissolved in 100 parts of dioxane and after adding 4 parts of copper acetate and 10 parts of tributylamine in an autoclave at room temperature under carbon dioxide pressure stirred for 30 at 8 hours, then heated to 100 "C within 8 hours and at held at this temperature for 12 hours. After filtering and evaporation of the solvent the residue is recrystallized from ethyl acetate.

52 parts of 3-isopropyl-5-methylene-4,4-dimethyl-oxazolidone- (2) are obtained of m.p. 125 to 127 "C.

Claims (2)

Claims: 1. Process for the preparation of 5-Methylenoxazolidonen- (2) of the general formula where R and R 'are hydrogen atoms or aliphatic, cycloaliphatic, araliphatic or aromatic radicals or jointly members of a cycloaliphatic ring and R "is a hydrogen atom or an aliphatic or araliphatic radical optionally substituted by indifferent groups, characterized in that acetylenamines of the general formula where R, R 'and R "have the abovementioned meaning, reacted with carbon dioxide under elevated pressure and at elevated temperature in the presence of copper salts. 2. The method according to claim 1, characterized in that the Implementation in the presence of tertiary amines.