3-(2-oxocyclohexyl)propanenitrile

反応条件: temp:55.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A reactor is loaded with 151 g of 3-(2-cyclohexanonyl)propionitrile in 500 ml of n-hexane and 260 g of m-chloroperbenzoic acid (70% titer) dissolved at 50° C. in 2000 ml of n-hexane in 30 minutes. The solution is heated to 55° C. for 15 hours. Cooling of the solution separates, in crystalline form, part of the m-chlorobenzoic acid which is scarcely soluble in the system, together with a heavy liquid phase which is formed by 7-cyanoethyl-2-oxepanone and by m-chlorobenzoic acid. 71.5 g of 7-cyanoethyl-2-oxepanone, impure with m-chlorobenzoic acid, are recovered from the lower phase. 24 g of 7-cyanoethyl-2-oxepanone are recovered from the upper phase by concentration and several crystallizations. Conversion over the initial ketone is 85%. Yield on the converted amount is 57%.

反応条件: temp:55.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A reactor is loaded with 151 g of 3-(2-cyclohexanonyl)propionitrile in 500 ml of n-hexane and 260 g of m-chloroperbenzoic acid (70% titer) dissolved at 50° C. in 2000 ml of n-hexane in 30 minutes. The solution is heated to 55° C. for 15 hours. Cooling of the solution separates, in crystalline form, part of the m-chlorobenzoic acid which is scarcely soluble in the system, together with a heavy liquid phase which is formed by 7-cyanoethyl-2-oxepanone and by m-chlorobenzoic acid. 71.5 g of 7-cyanoethyl-2-oxepanone, impure with m-chlorobenzoic acid, are recovered from the lower phase. 24 g of 7-cyanoethyl-2-oxepanone are recovered from the upper phase by concentration and several crystallizations. Conversion over the initial ketone is 85%. Yield on the converted amount is 57%.

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

実験手順: The chlorination of 2-oxo-1-cyclohexanepropionitrile takes place in a manner similar to that described above for the preparation of 2-tert-butyl-6-chloro-cyclohexanone. The title compound is reacted as a crude product without further characterization.

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

実験手順: The chlorination of 2-oxo-1-cyclohexanepropionitrile takes place in a manner similar to that described above for the preparation of 2-tert-butyl-6-chloro-cyclohexanone. The title compound is reacted as a crude product without further characterization.

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

実験手順: Through a tubular reactor (diameter 16 mm, packing height 50 cm, oil-heated double jacket), installed up-stream of the hydrogenation reactor and packed with 67.2 g (96 ml) of γ-aluminum oxide in the form of 1.5 mm extrudates, there were pumped upwardly, per hour, 22.6 g of 2-(2-cyanoethyl)-cyclohexanone (purity 96%, 0.144 mole) and 1,086 ml of liquid ammonia (652 g, 38.3 moles) at a pressure of 250 bar and a temperature of 70° C. Hydrogen was then added to the stream at a rate of 60 standard liters (2.7 moles) per hour, and the effluent from the in-line imination reactor was passed upwardly through the hydrogenation reactor at a pressure of 250 bar and a temperature of 120° C. Following separation and distillation of the product obtained after an on-stream period of 16.3 hours there were obtained, besides 43.5 g of decahydroquinoline, 291.7 g of 2-(3-aminopropyl)-cyclohexylamine. The yield of 2-(3-aminopropyl)-cyclohexylamine was 79.8% of theory. Through a tubular reactor (diameter 16 mm, packing height 50 cm, oil-heated double jacket) were pumped upwardly, per hour a temperature of 70° C the effluent from the in-line imination reactor was passed upwardly through the hydrogenation reactor at a pressure of 250 bar a temperature of 120° C separation and distillation of the product obtained after an on-stream period of 16.3 hours there

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

実験手順: Through a tubular reactor (diameter 16 mm, packing height 50 cm, oil-heated double jacket), installed upstream of the hydrogenation reactor and packed with 63.5 g (100 ml) of titanium dioxide (anatase) in the form of 1.5 mm extrudates, there were passed upwardly, per hour, 16.0 g of 2-(2-cyanoethyl)-cyclohexanone (purity 97.5%, 0.103 mole) and 51 g of liquid ammonia (87 ml, 3.0 moles) at a pressure of 250 bar and a temperature of 80° C. Hydrogen was then added to the stream at ar ate of 60 standard liters per hour, and the effluent from the in-line imination reactor was passed upwardly through the hydrogenation reactor at a pressure of 250 bar and a temperature of 130° C. The effluent was depressurized to standard pressure, and the ammonia was distilled off. Gas-chromatographic analysis of the hydrogenation product gave 92.5% of 2-(3-aminopropyl)-cyclohexylamine and 4.5% of decahydroquinoline. The effluent was collected over a period of 46 hours and fractionated by distillation in a 30 cm packed column containing 3 mm glass rings. There were obtained 674 g of 2-(3-aminopropyl)-cyclohexylamine, corresponding to a yield of 91.0% of theory. Through a tubular reactor (diameter 16 mm, packing height 50 cm, oil-heated double jacket) were passed upwardly, per hour a temperature of 80° C the effluent from the in-line imination reactor was passed upwardly through the hydrogenation reactor at a pressure of 250 bar a temperature of 130° C the ammonia was distilled off

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

実験手順: Through a tubular reactor (diameter 16 mm, packing height 50 cm, oil-heated double jacket), installed up-stream of the hydrogenation reactor and packed with 70.0 g (100 g) of γ-aluminum oxide in he form of 1.5 mm extrudates, there were passed upwardly, per hour, 10.7 g of 2-(2-cyanoethyl)-cyclohexanone (purity 97.5%, 0.069 mole) and 500 ml of liquid ammonia (300 g, 17.6 moles) at a pressure of 250 bar and a temperature of 80° C. Hydrogen was then added to the stream at a rate of 60 standard liters (2.7 moles) per hour, and the effluent from the in-line imination reactor was passed upwardly through the hydrogenation reactor at a pressure of 250 bar and a temperature of 130° C. Gas-chromatographic analysis of the hydrogenation product gave 86.3% of 2-(3-aminopropyl)-cyclohexylamine and 7.9% of decahydroquinoline, corresponding to a yield of 2-(3-aminopropyl)-cyclohexylamine of 87.1% of theory. Through a tubular reactor (diameter 16 mm, packing height 50 cm, oil-heated double jacket) form of 1.5 mm extrudates, there were passed upwardly, per hour a temperature of 80° C the effluent from the in-line imination reactor was passed upwardly through the hydrogenation reactor at a pressure of 250 bar a temperature of 130° C

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

実験手順: Example 3 was repeated except that 29.7 g of 2-(2-cyanoethyl)-cyclohexanone (purity 96%, 0.189 mole) and 1,200 ml of liquid ammonia (720 g, 42.4 moles) were passed upwardly through the first reactor, per hour, at a pressure of 250 bar and a temperature of 70° C. Hydrogen was then added to the stream at a rate of 125 standard liters (5.6 moles) per hour, and the effluent from the in-line imination reactor was passed upwardly through the hydrogenation reactor at a pressure of 250 bar and a temperature of 125° C. After an on-stream time of 17.8 hours the separation and distillation measures as per Example 2 had yielded, besides 66.4 g of decahydroquinoline, 365 g of 2-(3-aminopropyl)-cyclohexylamine. The yield of 2-(3-aminopropyl)-cyclohexylamine was 69.7% of theory. were passed upwardly through the first reactor, per hour, at a pressure of 250 bar a temperature of 70° C the effluent from the in-line imination reactor was passed upwardly through the hydrogenation reactor at a pressure of 250 bar a temperature of 125° C After an on-stream time of 17.8 hours the separation and distillation measures as per Example 2

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

実験手順: Through a tubular reactor (diameter 16 mm, packing height 50 cm, oil-heated double jacket), installed up-stream of the hydrogenation reactor and packed with 64.4 g (92 ml) of γ-aluminum oxide there were passed upwardly, per hour, 55.4 g of 2-(2-cyanoethyl)-cyclohexanone (purity 96%, 0.352 mole) and 875 ml of liquid ammonia (525 g, 30.9 moles) at a pressure of 250 bar and a temperature of 70° C. Hydrogen was then added to the stream at a rate of 200 standard liters (8.9 moles) per hour, and the effluent from the in-line imination reactor was passed upwardly through the hydrogenation reactor at a pressure of 250 bar and a temperature of 120° C. After an on-stream of 3.5 hours the separation and distillation measures as per Example 2 had yielded, besides 33.1 g of decahydroquinoline, 138.8 of 2-(3-aminopropyl)-cyclohexylamine, this corresponding to a yield of 2-(3-aminopropyl)-cyclohexylamine of 71.5% of theory. Through a tubular reactor (diameter 16 mm, packing height 50 cm, oil-heated double jacket) there were passed upwardly, per hour a temperature of 70° C the effluent from the in-line imination reactor was passed upwardly through the hydrogenation reactor at a pressure of 250 bar a temperature of 120° C After an on-stream of 3.5 hours the separation and distillation measures as per Example 2

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

実験手順: Through a tubular reactor (diameter 16 mm, packing height 50 cm, oil-heated double jacket), installed up-stream of the hydrogenation reactor and packed with 67.2 g (96 ml) of γ-aluminum oxide in the form of 1.5 mm extrudates, there were pumped upwardly, per hour, 22.6 g of 2-(2-cyanoethyl)-cyclohexanone (purity 96%, 0.144 mole) and 1,086 ml of liquid ammonia (652 g, 38.3 moles) at a pressure of 250 bar and a temperature of 70° C. Hydrogen was then added to the stream at a rate of 60 standard liters (2.7 moles) per hour, and the effluent from the in-line imination reactor was passed upwardly through the hydrogenation reactor at a pressure of 250 bar and a temperature of 120° C. Following separation and distillation of the product obtained after an on-stream period of 16.3 hours there were obtained, besides 43.5 g of decahydroquinoline, 291.7 g of 2-(3-aminopropyl)-cyclohexylamine. The yield of 2-(3-aminopropyl)-cyclohexylamine was 79.8% of theory. Through a tubular reactor (diameter 16 mm, packing height 50 cm, oil-heated double jacket) were pumped upwardly, per hour a temperature of 70° C the effluent from the in-line imination reactor was passed upwardly through the hydrogenation reactor at a pressure of 250 bar a temperature of 120° C separation and distillation of the product obtained after an on-stream period of 16.3 hours there

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

実験手順: Through a tubular reactor (diameter 16 mm, packing height 50 cm, oil-heated double jacket), installed up-stream of the hydrogenation reactor and packed with 41.6 g (92 ml) of a zeolite type Y which had been extruded with Aerosil 200 (ratio Y-type zeolite to Aerosil 200 9:1, ratio SiO2 to Al2O3 6:1), there were passed upwardly, per hour, 36.7 g of 2-(2-cyanoethyl)-cyclohexanone (purity 96%, 0.233 mole) and 1.475 ml of liquid ammonia (885 g, 52.1 moles) at a pressure of 250 bar and a temperature of 70° C. Hydrogen was then added to the stream at a rate of 150 standard liters (6.7 moles) per hour, and the effluent from this in-line imination reactor was passed upwardly through the hydrogenation reactor at a pressure of 250 bar and a temperature of 120° C. The product mixture was depressurized to standard pressure and fed to the top of a column (length 46 cm, diameter 3 cm) held at 40° C. and packed with 5 mm wire mesh rings in which the ammonia was removed. After an on-stream time of 19.9 hours distillation of the product had yielded, besides 189.7 g of decahydroquinoline, 431.2 g of 2-(3-aminopropyl)-cyclohexylamine, this corresponding to a yield of 2-(3-aminopropyl)-cyclohexylamine of 59.6% of theory. Through a tubular reactor (diameter 16 mm, packing height 50 cm, oil-heated double jacket) were passed upwardly, per hour a temperature of 70° C the effluent from this in-line imination reactor was passed upwardly through the hydrogenation reactor at a pressure of 250 bar a temperature of 120° C held at 40° C. was removed After an on-stream time of 19.9 hours distillation of the product

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

実験手順: Through a tubular reactor (diameter 16 mm, packing height 50 cm, oil-heated double jacket), installed up-stream of the hydrogenation reactor and packed with 41.6 g (92 ml) of a zeolite type Y which had been extruded with Aerosil 200 (ratio Y-type zeolite to Aerosil 200 9:1, ratio SiO2 to Al2O3 6:1), there were passed upwardly, per hour, 36.7 g of 2-(2-cyanoethyl)-cyclohexanone (purity 96%, 0.233 mole) and 1.475 ml of liquid ammonia (885 g, 52.1 moles) at a pressure of 250 bar and a temperature of 70° C. Hydrogen was then added to the stream at a rate of 150 standard liters (6.7 moles) per hour, and the effluent from this in-line imination reactor was passed upwardly through the hydrogenation reactor at a pressure of 250 bar and a temperature of 120° C. The product mixture was depressurized to standard pressure and fed to the top of a column (length 46 cm, diameter 3 cm) held at 40° C. and packed with 5 mm wire mesh rings in which the ammonia was removed. After an on-stream time of 19.9 hours distillation of the product had yielded, besides 189.7 g of decahydroquinoline, 431.2 g of 2-(3-aminopropyl)-cyclohexylamine, this corresponding to a yield of 2-(3-aminopropyl)-cyclohexylamine of 59.6% of theory. Through a tubular reactor (diameter 16 mm, packing height 50 cm, oil-heated double jacket) were passed upwardly, per hour a temperature of 70° C the effluent from this in-line imination reactor was passed upwardly through the hydrogenation reactor at a pressure of 250 bar a temperature of 120° C held at 40° C. was removed After an on-stream time of 19.9 hours distillation of the product