DE1125443B - Process for the preparation of optionally etherified 5-oxymethyltetrahydrofurfuryl- (2) -amines - Google Patents

Description

Process for the preparation of optionally etherified 5-oxymethyltetrahydrofurfuryl- (2) -amines The invention relates to a process for the production of optionally etherified 5-Oxymethyltetrahydrofurfuryl- (2) -amines, which can be substituted on the nitrogen.

According to the invention, these compounds are prepared in such a way that 5-oxymethylfurfurol or its n-octyl ether in an organic solvent with ammonia, an aliphatic primary or secondary amine, or ethanolamine and hydrogen in the presence of a catalyst, particularly Raney nickel Overpressure and higher temperature are hydrogenated in the core and in a manner known per se aminated at the same time reducing.

The compounds prepared according to the invention are known to be surface-active Agent and usable as a detergent for acid gases.

5 - Oxymethyltetrahydrofurfuryl - (2) - amine is a water-clear, practically odorless liquid. It is an excellent solvent for dried paint films and for a wide variety of organic substances.

The surprising effect of the process according to the invention produced 5-oxymethyltetrahydrofurfuryl- (2) -amine as a detergent for carbonic acid gas with changing partial pressure compared to monoethanolamine results from the following attempts. The two experiments were done with 3.3 and 1.57 molar concentrations, respectively the connection used.

Absorption of carbon dioxide by 5-oxymethyltetrahydrofurfuryl- (2) -amine (called A for short) or by monoethanolamine Partial pressure Mol COZ / MolA Moles of CO2 / mole Monoethanolamine 1. 3.3 mol A or monoethanolamine at 65 ° C 30 0.35 0.46 115 0.722 0.53 180 0.826 0.54 200 0.863 0.55 2. 1.57 mol A or monoethanolamine at 65 ° C 30 0.36 II 0.41 115 0.750 0.57 These values show that the 5-oxymethyltetrahydrofurfuryl - (2) - amine at higher pressures, as used in the art for removing carbon dioxide in the production of e.g. B. pure nitrogen are common - is much more effective than monoethanolamine.

The following examples explain the process according to the invention.

Example 1 5-Oxymethyltetrahydrofurfuryl- (2) -amine In a solution of 50 g (0.395 mol) of distilled 5-oxymethylfurfurol in 135 cc of methanol were added 20 cc of liquid ammonia (15.2 g = 0.9 mol) and 11/4 teaspoons of Raney -Nickel registered. The mixture was heated to 150 ° C (with shaking) for 10 hours under a hydrogen pressure of 386.7 to 421.8 kg / cm2, then the reaction mixture was cooled, the catalyst was filtered off, and the volatiles were removed on the steam bath. The dark-colored residue was distilled at 0.08 mm mercury pressure, at which pressure the reaction product passed over at 76.6 to 81.8 ° C. Three fractions were collected, namely: 3.90 g, n 2D1 = 1.4870; 23.69 gn 1D1 = 1.4872, and 13.59 g, n 1ö1 = 1.4868, which were then combined. The yield of 5-oxymethyltetrahydrofurfuryl- (2) -amine in the form of a viscous, water-clear liquid with n 2p2 = 1.4870 and the density d = 1.1008 was 41.18 g (79.5%).

Example 2 5-Oxymethyltetrahydrofurfuryl- (2) -ethylamine A mixture of 25.2 g (0.2 mol) of distilled 5-oxymethylfurfurol and 63.5 g of a 70 ° / jgen A solution of ethylamine in methanol was introduced into 66.7 cc of methanol with cooling. The dark colored mixture was mixed with 1 teaspoon of Raney nickel and the Mixture heated to 150 ° C for 20 hours under a hydrogen pressure of 421.8 kg / cm2.

After cooling the reaction mixture, the catalyst was from the light yellow reaction solution filtered off and the filtrate after removal of the methanol distilled. There were 24.5 g (77.10 /,) of 5-oxymethyltetrahydrofurfuryl- (2) ethylamine obtained from b.p. 220 72 to 75 ° C and nD = 1.4709.

Example 3 5-Oxymethyltetrahydrofurfuryl- (2) -diethylamine A mixture of 25.2 g (0.2 mol) of 5-oxymethylfurfural and 35 cc of methanol was mixed with 73.1 g (107 ccm = 1 mol) of freshly distilled diethylamine were added, the mixture warming up and colored considerably darker. Then the mixture was made with 1 teaspoon of Raney nickel added and 12 hours at 150 ° C under a hydrogen pressure of 351.5 to 421.8 kg / cm2 held.

The reaction mixture was then cooled and the catalyst was filtered off and the solvent and the excess diethylamine are distilled off in vacuo. The residue was distilled under a pressure of 0.20 mm of mercury. The yield of 5-oxymethyltetrahydrofurfuryl (2) diethylamine which passes over at 77 to 78.5 ° C was 14.71 g (39.4%), n ö = 1.4650. The connection creates a strongly hygroscopic, water-clear liquid with a faint odor and a strong alkaline reaction.

Example 4 5-Oxymethyltetrahydrofurfuryl- (2) -ethanolamine Teaspoon of Raney nickel and heated to 150 ° C for 20 hours under a hydrogen pressure of 351.5 to 421.8 kg / cm2. The catalyst was then filtered off and the excess ethanolamine was distilled off. As a reaction product were 29.05 g of a fraction of bp. Get "5 71-145 'C which was redistilled at a pressure of 200 mm mercury. The in-aoo Kp.2oo 135-143 ° C, n = 2œ3 1, 4922, the transferring fraction is 5-oxymethyltetrahydrofurfuryl- (2) -ethanolamine. Yield: 13.43 g = 35.2% of theory.

Example 5 n-Octyloxymethyltetrahydrofurfuryl- (2) -amine 2.38 parts (0.01 mol) n-octyl ether of 5-oxymethylfurfurol were mixed with Raney nickel in the presence of 5 parts of methanol and 10 parts of ammonia for 20 hours under hydrogen pressure of 421.8 kg / cm 'at 150 ° C in a rocking autoclave reducing aminated. That The analysis of liquid product gave the correct values for 5-n-octyloxymethyltetrahydrofurfuryl- (2) -amine from bp 4.152 to 154 ° C, na3 = 1.4539. The yield was 1.22 parts = 50% the theory.

Example 6 5-Oxymethyltetrahydrofurfuryl- (2) -isopropylamine In a A solution of 121 g (1.2 mol) of 5-oxymethylfurfural in 300 cc of methanol was 212 g (3.6 mol) isopropylamine and 10 g Raney nickel entered. The mixture was under heated to 100 ° C for 20 hours under a hydrogen pressure of 421.8 kg / cm2, then cooled, the catalyst was filtered off and the volatiles were distilled off. Of the The residue was distilled and the distillation was stopped at a boiling point of 85 to 88 ° C. 170 g = 820/0 of the theory 5-oxymethyltetrahydrofurfuryl- (2) -isopropylamine, rz 2a3 = 1.4690.

Example 7 5-Oxymethyltetrahydrofurfuryl- (2) -butylamine According to the method described in Example 6, 129 g of butylamine were reacted with 25.2 g of 5-oxymethylfurfurol dissolved in 67 cc of methanol in the presence of 1 teaspoon of Raney nickel. The reaction was carried out for 15 hours at 150 ° C under a hydrogen pressure of 351.5 to 421.8 kg / cm 2. The yield of the 5-oxymethyltetrahydrofurfuryl- (2) -butylamine passing over at bp 4.96.4 to 99 ° C. was 14.0 g = 540 /, of theory. n2D ° = 1.4693.

Example 8 5-Oxymethyltetrahydrofurfuryl- (2) -hexylamine According to the method described in Example 2, 101 g of n-hexylamine were reacted with 25.2 g of 5-oxymethylfurfurol dissolved in 67 cc of methanol in the presence of 1 teaspoon of Raney nickel. The reaction was carried out for 6 hours at 200 ° C. under a hydrogen pressure of 281.2 kg / cm '. 168.5 g = 73% of theory of 5-oxymethyltetrahydrofurfuryl- (2) -hexylamine with a boiling point of 103 to 105 ° C., nD = 1.4681.

Claims (1)

PATENT CLAIM: Process for the preparation of optionally vexetherified 5-oxymethyltetrahydrofurfuryl- (2) -amines, which can be substituted on nitrogen, of the general formula in which R 1 and R 1 are hydrogen atoms, alkyl or β-oxyethyl groups and R 3 is an oxy group or n-octyloxy group, characterized in that 5-oxymethylfurfural or its n-octyl ether is used in an organic solvent with ammonia, an aliphatic primary or secondary amine or ethanolamine and hydrogen in the presence of a catalyst, in particular Raney nickel, hydrogenated in a manner known per se in the core at excess pressure and higher temperature and at the same time aminated in a reducing manner. Publications considered: Comptes rendus, 221, pp. 560-561 (1945).