3-(2-cyanoethylamino)propanenitrile

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Bis(2-cyanoethyl)amine (3.0 g, 0.0224 mole) was added with ethyl acetate (15 ml) and anhydrous magnesium sulfate (3 g), and the mixture was stirred at room temperature. A solution of methyltrioxorhenium (0.0183 g, 0.0734 mmole) dissolved in 35% aqueous hydrogen peroxide (2.9 g, 0.029 mole) was added dropwise to the mixture while internal temperature was kept at from 20° C. to 30° C. After the reaction mixture was stirred at room temperature for 1 hour, the magnesium sulfate was removed by filtration, and the filtrate was added with a solution of oxalic acid (2.2 g, 0.224 mole) dissolved in acetone (8 ml). The mixture was stirred for 30 minutes under ice cooling, and the precipitated crystals were collected by filtration to obtain oxalic acid salt of N,N-bis(2-cyanoethyl)hydroxylamine (4.2 g, yield: 75.0%) having melting point of 129-130° C. Chemical structure of the product was analyzed by 1H-NMR, mass spectrometry and elemental analysis. 1H-NMR (DMSO-D6) σ (ppm) (multiplicity, integrated value): 12.0-9.50 (br, 2H), 2.77 (t, 4H), 2.58 (t, 4H). Elemental analysis, calculated for C8H11N3O5 : C, 41.92; H, 4.84; N, 18.33, found: C, 42.50; H, 4.74; N, 18.38. was added dropwise to the mixture while internal temperature was kept at from 20° C. to 30° C After the reaction mixture was stirred at room temperature for 1 hour the magnesium sulfate was removed by filtration The mixture was stirred for 30 minutes under ice cooling the precipitated crystals were collected by filtration

反応条件: temp:95.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A 300 cc Hastelloy C autoclave was charged with 10.0 g of 5% palladium on carbon catalyst (50 wt % water wet). The reactor was flushed several times with nitrogen and then hydrogen. Then 123 g of crude IBPN obtained as the distillation residue in Example 1 was pumped into the autoclave. The temperature of the reactor contents was raised to 95°C. and hydrogen was added to provide a pressure of 115 psig. Formaldehyde (as a 55 wt % solution in methanol) was then admitted to the autoclave at a rate of 0.2 ml/min until a total of 66.9 g had been added. The mixture was allowed to react for 3.5 hours at which time analysis by gas chromatography/mass spectroscopy revealed that the IBPN had been completely converted to methyliminobispropionitrile (MIBPN). The reactor contents containing the MIBPN were then cooled and filtered and the methanol and water were removed in vacuo to give a clear light yellow liquid. Little to no reduction of the nitrile to the amine occurred under these conditions as evidenced by the lack of terminal N-methyl derivatives in the GC mass spectrum. The reactor was flushed several times with nitrogen Then 123 g of crude IBPN obtained as the distillation residue in Example 1 to provide a pressure of 115 psig had been added to react for 3.5 hours at which time analysis by gas chromatography/mass spectroscopy were then cooled filtered the methanol and water were removed in vacuo to give a clear light yellow liquid

反応条件: temp:95.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A 300 cc Hastelloy C autoclave was charged with 10.0 g of 5% palladium on carbon catalyst (50 wt % water wet). The reactor was flushed several times with nitrogen and then hydrogen. Then 123 g of crude IBPN obtained as the distillation residue in Example 1 was pumped into the autoclave. The temperature of the reactor contents was raised to 95°C. and hydrogen was added to provide a pressure of 115 psig. Formaldehyde (as a 55 wt % solution in methanol) was then admitted to the autoclave at a rate of 0.2 ml/min until a total of 66.9 g had been added. The mixture was allowed to react for 3.5 hours at which time analysis by gas chromatography/mass spectroscopy revealed that the IBPN had been completely converted to methyliminobispropionitrile (MIBPN). The reactor contents containing the MIBPN were then cooled and filtered and the methanol and water were removed in vacuo to give a clear light yellow liquid. Little to no reduction of the nitrile to the amine occurred under these conditions as evidenced by the lack of terminal N-methyl derivatives in the GC mass spectrum. The reactor was flushed several times with nitrogen Then 123 g of crude IBPN obtained as the distillation residue in Example 1 to provide a pressure of 115 psig had been added to react for 3.5 hours at which time analysis by gas chromatography/mass spectroscopy were then cooled filtered the methanol and water were removed in vacuo to give a clear light yellow liquid

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: This example shows even at the high mole ratio of ammonia to acrylonitrile (7:1) substantial cyanoethylation of APN occurred resulting in large quantities of iminobispropionitrile.

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The reaction takes place in a tube reactor which has an internal diameter of 36 mm and a length of 70 cm. At the lower end of the reactor there is a glass frit G 4, manufactured by the Schott Company, Mainz. It is designated 160 D and has a 30 mm diameter. The glass frit functions as a distribution device. The tube has a total volume of 700 ml. and the effective reaction volume (the space used during the reaction) equals 500 ml. 9 liters of gaseous ammonia are fed into the reactor per hour. The gas flows through the glass frit and reacts with the acrylonitrile. In order to monitor the gas conversion, the amount of unreacted gas is determined using a gas meter. 52 ml of acrylonitrile and 3.8 ml of water are pumped hourly into the upper end of the reactor at a rate which corresponds to a space velocity of 0.1 hr-1. After 10 hours of residence time, the reaction mixture is removed at a point above the distribution device located at the lower end of the tube reactor. The yield of bis-(2-cyanoethyl)-amine obtained is 91 %. and the effective reaction volume (the space used during the reaction) corresponds to a space velocity of 0.1 hr the reaction mixture is removed at a point above the distribution device

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: It is advantageous to introduce the acrylonitrile into the reactor at a space velocity of about 0.05 to 0.6 hr-1. Simultaneously, a gaseous ammonia charge is introduced into the reactor via a distribution device; e.g. a frit at the lower floor of the column, preferably in such an amount that the acrylonitrile and ammonia flow through the reaction chamber at a mole ratio of 2 : 1. According to the method of the present invention, the ammonia is completely absorbed as the gas bubbles rise. Furthermore, the ascending gas bubbles insure an intimate mixing of the reactants and thus an immediate reaction occurs resulting in the formation of bis-(2-cyanoethyl)-amine. The reaction product is removed at the lower end of the reactor above the distribution device. It is recovered as a clear liquid with a water content between 8 and 15% depending on the water concentration in the acrylonitrile. The yields obtained are greater than 90%. is introduced into the reactor via a distribution device the ammonia is completely absorbed as the gas bubbles rise an intimate mixing of the reactants thus an immediate reaction

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: It is advantageous to introduce the acrylonitrile into the reactor at a space velocity of about 0.05 to 0.6 hr-1. Simultaneously, a gaseous ammonia charge is introduced into the reactor via a distribution device; e.g. a frit at the lower floor of the column, preferably in such an amount that the acrylonitrile and ammonia flow through the reaction chamber at a mole ratio of 2 : 1. According to the method of the present invention, the ammonia is completely absorbed as the gas bubbles rise. Furthermore, the ascending gas bubbles insure an intimate mixing of the reactants and thus an immediate reaction occurs resulting in the formation of bis-(2-cyanoethyl)-amine. The reaction product is removed at the lower end of the reactor above the distribution device. It is recovered as a clear liquid with a water content between 8 and 15% depending on the water concentration in the acrylonitrile. The yields obtained are greater than 90%. is introduced into the reactor via a distribution device the ammonia is completely absorbed as the gas bubbles rise an intimate mixing of the reactants thus an immediate reaction

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 3,3′-iminodipropionitrile (1.50 g, 12.18 mmol) and thiosemicarbazide (2.22 g, 24.36 mmol) in TFA (10 mL) was heated at 85 for 4.5 h. The reaction was cooled to room temperature and poured into a mixture of ice and water. Sodium hydroxide pellets were added to the mixture until it was basic (pH 14). The white precipitate was collected by suction filtration, rinsed with water and dried to provide 5-(2-((2-(5-amino-1,3,4-thiadiazol-2-yl)ethyl)amino)ethyl)-1,3,4-thiadiazol-2-amine (1005, 1.47 g). 1H NMR (300 MHz, DMSO-d6) δ 6.95 (s, 4H), 2.90 (d, J=6.0 Hz, 4H), 2.83 (d, J=6.3 Hz, 4H). was heated at 85 for 4.5 h The white precipitate was collected by suction filtration rinsed with water dried

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 3,3′-iminodipropionitrile (1.50 g, 12.18 mmol) and thiosemicarbazide (2.22 g, 24.36 mmol) in TFA (10 mL) was heated at 85 for 4.5 h. The reaction was cooled to room temperature and poured into a mixture of ice and water. Sodium hydroxide pellets were added to the mixture until it was basic (pH 14). The white precipitate was collected by suction filtration, rinsed with water and dried to provide 5-(2-((2-(5-amino-1,3,4-thiadiazol-2-yl)ethyl)amino)ethyl)-1,3,4-thiadiazol-2-amine (1005, 1.47 g). 1H NMR (300 MHz, DMSO-d6) δ 6.95 (s, 4H), 2.90 (d, J=6.0 Hz, 4H), 2.83 (d, J=6.3 Hz, 4H). was heated at 85 for 4.5 h The white precipitate was collected by suction filtration rinsed with water dried

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Bis(2-cyanoethyl)amine (3.0 g, 0.0224 mole) was added with ethyl acetate (15 ml) and anhydrous magnesium sulfate (3 g), and the mixture was stirred at room temperature. A solution of methyltrioxorhenium (0.0183 g, 0.0734 mmole) dissolved in 35% aqueous hydrogen peroxide (2.9 g, 0.029 mole) was added dropwise to the mixture while internal temperature was kept at from 20° C. to 30° C. After the reaction mixture was stirred at room temperature for 1 hour, the magnesium sulfate was removed by filtration, and the filtrate was added with a solution of oxalic acid (2.2 g, 0.224 mole) dissolved in acetone (8 ml). The mixture was stirred for 30 minutes under ice cooling, and the precipitated crystals were collected by filtration to obtain oxalic acid salt of N,N-bis(2-cyanoethyl)hydroxylamine (4.2 g, yield: 75.0%) having melting point of 129-130° C. Chemical structure of the product was analyzed by 1H-NMR, mass spectrometry and elemental analysis. 1H-NMR (DMSO-D6) σ (ppm) (multiplicity, integrated value): 12.0-9.50 (br, 2H), 2.77 (t, 4H), 2.58 (t, 4H). Elemental analysis, calculated for C8H11N3O5 : C, 41.92; H, 4.84; N, 18.33, found: C, 42.50; H, 4.74; N, 18.38. was added dropwise to the mixture while internal temperature was kept at from 20° C. to 30° C After the reaction mixture was stirred at room temperature for 1 hour the magnesium sulfate was removed by filtration The mixture was stirred for 30 minutes under ice cooling the precipitated crystals were collected by filtration

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Bis(2-cyanoethyl)amine (3.0 g, 0.0224 mole) was added with ethyl acetate (15 ml) and anhydrous magnesium sulfate (3 g), and the mixture was stirred at room temperature. A solution of methyltrioxorhenium (0.0183 g, 0.0734 mmole) dissolved in 35% aqueous hydrogen peroxide (2.9 g, 0.029 mole) was added dropwise to the mixture while internal temperature was kept at from 20° C. to 30° C. After the reaction mixture was stirred at room temperature for 1 hour, the magnesium sulfate was removed by filtration, and the filtrate was added with a solution of oxalic acid (2.2 g, 0.224 mole) dissolved in acetone (8 ml). The mixture was stirred for 30 minutes under ice cooling, and the precipitated crystals were collected by filtration to obtain oxalic acid salt of N,N-bis(2-cyanoethyl)hydroxylamine (4.2 g, yield: 75.0%) having melting point of 129-130° C. Chemical structure of the product was analyzed by 1H-NMR, mass spectrometry and elemental analysis. 1H-NMR (DMSO-D6) σ (ppm) (multiplicity, integrated value): 12.0-9.50 (br, 2H), 2.77 (t, 4H), 2.58 (t, 4H). Elemental analysis, calculated for C8H11N3O5 : C, 41.92; H, 4.84; N, 18.33, found: C, 42.50; H, 4.74; N, 18.38. was added dropwise to the mixture while internal temperature was kept at from 20° C. to 30° C After the reaction mixture was stirred at room temperature for 1 hour the magnesium sulfate was removed by filtration The mixture was stirred for 30 minutes under ice cooling the precipitated crystals were collected by filtration