(2Z)-N,N-diethyl-3,7-dimethylocta-2,6-dien-1-amine

反応条件: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 11.37 g (50 mmol) of (Z)-N,N-diethyl-3,7-dimethyl-2,6-octadienylamine, 101.5 mg (0.25 mmol) of bis[η4 -(Z,Z)-1,5-cyclooctadiene]rhodium(I) tetrafluoroborate, 160 mg (0.275 mmol) of (R)-(6,6'-dimethoxybiphenyl-2,2'-diyl)bis(diphenylphosphine) and 25 ml of tetrahydrofuran was heated to 65° C. while stirring for 20 hours. The brownish-red reaction mixture was evaporated and the residue was distilled in a bulb-tube at about 150° C./0.2 mbar, whereby 10.7 g of (1E,3R)-N,N-diethyl-3,7-dimethyl-1,6-octadienylamine were obtained as a light yellowish oil. The distillate was diluted with 20 ml of hexane, treated with 50 ml of 50% acetic acid and the two-phase mixture was stirred vigorously for 1 hour. After working-up in an analogous manner to Example 14 and distillation in a bulb-tube at 140° C./15 mbar there were obtained 7.18 g of (R)-citronellal as a colourless liquid: e.e=98.6% The brownish-red reaction mixture was evaporated the residue was distilled in a bulb-tube at about 150° C./0.2 mbar

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

実験手順: A mixture of 2.27 g (10.0 mmol) of (Z)-N,N-diethyl-3,7-dimethyl-2,6-octadienylamine, 36 mg (0.041 mmol) of [θ4 -(Z,Z)-1,5-cyclooctadiene][(R)-6,6'-dimethoxybiphenyl-2,2'-diyl)bis(diphenylphosphine)]rhodium(I) tetrafluoroborate and 5 ml of tetrahydrofuran was heated to 85°-90° C. for 16 hours in a sealed tube. The brownish reaction mixture was evaporated and the residue was distilled in a bulb-tube at about 150° C./0.2 mbar, whereby 2.1 g of (1E, 3R)-N,N-diethyl-3,7-dimethyl-1,6-octadienylamine were obtained as a colourless oil. The distillate obtained was diluted with hexane, treated with 5 ml of 50% acetic acid and the mixture was stirred for 1 hour. The phases were separated and the organic phase was washed with water. 1N HCl, saturated NaHCO3 solution and saturated NaCl solution, dried over Na2SO4, filtered and evaporated. After distillation in a bulb-tube at about 130° C./15 mbar there were obtained 1.38 g (90%) of (R)-citronellal [(R)-3,7-dimethyl-6-octenal] as a colourless liquid. was heated to 85°-90° C. for 16 hours in a sealed tube The brownish reaction mixture was evaporated the residue was distilled in a bulb-tube at about 150° C./0.2 mbar

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

実験手順: A solution prepared by mixing 2.93 g (40.0 mmol) of diethylamine with 18.0 ml (180 mmol) of isoprene was introduced into a 100-ml pressure tube in a nitrogen atmosphere- Thereto was gradually added dropwise at 0° C. a solution (1.6 M solution) prepared by dissolving 0.064 g of n-butyllithium (1.0 mmol) in 0.63 ml of hexane. This mixture was stirred first at room temperature for 15 minutes and then at 90° C. for 2.5 hours. To the resultant reaction mixture was added 0.3 ml of water to deactivate the catalyst. After liquid separation, the organic layer was separated and distilled to recover the unreacted isoprene. Subsequently, the concentrate remaining after the isoprene recovery was distilled under reduced pressure to obtain 7.29 g (34.8 mmol; GC yield, 87.0%) of the target mixture comprising α-neryldiethylamine and neryldiethylamine. A solution prepared was introduced into a 100-ml pressure tube in a nitrogen prepared at 90° C. for 2.5 hours To the resultant reaction mixture After liquid separation the organic layer was separated distilled to recover the unreacted isoprene was distilled under reduced pressure to obtain

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

実験手順: 1.14 g (5.0 mmol) of (Z)-N,N-diethyl-3,7-dimethyl-2,6-octadienylamine, 5 ml of tetrahydrofuran and 16 mg (0.0192 mmol) of [η4 -bicyclo[2.2.1]hepta-2,5-diene][(R)-(6,6'-dimethyl-2,2'-biphenylylene)-bis(diphenylphosphine)]rhodium (I) tetrafluoroborate were placed in a Pyrex bomb tube under nitrogen. After degasifying the mixture, the tube was sealed and heated in a bomb tube oven at 85° C. to 90° C. for 19 hours. The brownish-red mixture was evaporated and the residue was distilled in a bulb-tube at about 120° C./0.05 mmHg. There were obtained 1.09 g of (1E,3R)-N,N-diethyl-3,7-dimethyl-1,6-octadienylamine as a colourless distillate. the tube was sealed heated in a bomb tube oven at 85° C. to 90° C. for 19 hours The brownish-red mixture was evaporated the residue was distilled in a bulb-tube at about 120° C./0.05 mmHg

反応条件: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 11.37 g (50 mmol) of (Z)-N,N-diethyl-3,7-dimethyl-2,6-octadienylamine, 101.5 mg (0.25 mmol) of bis[η4 -(Z,Z)-1,5-cyclooctadiene]rhodium(I) tetrafluoroborate, 160 mg (0.275 mmol) of (R)-(6,6'-dimethoxybiphenyl-2,2'-diyl)bis(diphenylphosphine) and 25 ml of tetrahydrofuran was heated to 65° C. while stirring for 20 hours. The brownish-red reaction mixture was evaporated and the residue was distilled in a bulb-tube at about 150° C./0.2 mbar, whereby 10.7 g of (1E,3R)-N,N-diethyl-3,7-dimethyl-1,6-octadienylamine were obtained as a light yellowish oil. The distillate was diluted with 20 ml of hexane, treated with 50 ml of 50% acetic acid and the two-phase mixture was stirred vigorously for 1 hour. After working-up in an analogous manner to Example 14 and distillation in a bulb-tube at 140° C./15 mbar there were obtained 7.18 g of (R)-citronellal as a colourless liquid: e.e=98.6% The brownish-red reaction mixture was evaporated the residue was distilled in a bulb-tube at about 150° C./0.2 mbar

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

実験手順: A mixture of 2.27 g (10.0 mmol) of (Z)-N,N-diethyl-3,7-dimethyl-2,6-octadienylamine, 36 mg (0.041 mmol) of [θ4 -(Z,Z)-1,5-cyclooctadiene][(R)-6,6'-dimethoxybiphenyl-2,2'-diyl)bis(diphenylphosphine)]rhodium(I) tetrafluoroborate and 5 ml of tetrahydrofuran was heated to 85°-90° C. for 16 hours in a sealed tube. The brownish reaction mixture was evaporated and the residue was distilled in a bulb-tube at about 150° C./0.2 mbar, whereby 2.1 g of (1E, 3R)-N,N-diethyl-3,7-dimethyl-1,6-octadienylamine were obtained as a colourless oil. The distillate obtained was diluted with hexane, treated with 5 ml of 50% acetic acid and the mixture was stirred for 1 hour. The phases were separated and the organic phase was washed with water. 1N HCl, saturated NaHCO3 solution and saturated NaCl solution, dried over Na2SO4, filtered and evaporated. After distillation in a bulb-tube at about 130° C./15 mbar there were obtained 1.38 g (90%) of (R)-citronellal [(R)-3,7-dimethyl-6-octenal] as a colourless liquid. was heated to 85°-90° C. for 16 hours in a sealed tube The brownish reaction mixture was evaporated the residue was distilled in a bulb-tube at about 150° C./0.2 mbar

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

実験手順: A solution prepared by mixing 2.93 g (40.0 mmol) of diethylamine with 18.0 ml (180 mmol) of isoprene was introduced into a 100-ml pressure tube in a nitrogen atmosphere. Thereto was gradually added dropwise at 0° C. a solution (1.6 M solution) prepared by dissolving 0.064 g of n-butyllithium (1.0 mmol) in 0.63 ml of hexane. This mixture was stirred first at room temperature for 15 minutes and then at 90° C. for 2.5 hours. To the resultant reaction mixture was added 0.3 ml of water to deactivate the catalyst. After liquid separation, the organic layer was separated and distilled to recover the unreacted isoprene. Subsequently, the concentrate remaining after the isoprene recovery was distilled under reduced pressure to obtain 7.29 g (34.8 mmol; GC yield, 87.0%) of the target mixture comprising α-neryldiethylamine and neryldiethylamine. Boiling point, 83-85° C./400 Pa. Neryldiethylamine A solution prepared was introduced into a 100-ml pressure tube in a nitrogen atmosphere prepared at 90° C. for 2.5 hours To the resultant reaction mixture After liquid separation the organic layer was separated distilled to recover the unreacted isoprene was distilled under reduced pressure to obtain

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

実験手順: A solution prepared by mixing 2.93 g (40.0 mmol) of diethylamine with 18.0 ml (180 mmol) of isoprene was introduced into a 100-ml pressure tube in a nitrogen atmosphere. Thereto was gradually added dropwise at 0° C. a solution (1.6 M solution) prepared by dissolving 0.064 g of n-butyllithium (1.0 mmol) in 0.63 ml of hexane. This mixture was stirred first at room temperature for 15 minutes and then at 90° C. for 2.5 hours. To the resultant reaction mixture was added 0.3 ml of water to deactivate the catalyst. After liquid separation, the organic layer was separated and distilled to recover the unreacted isoprene. Subsequently, the concentrate remaining after the isoprene recovery was distilled under reduced pressure to obtain 7.29 g (34.8 mmol; GC yield, 87.0%) of the target mixture comprising α-neryldiethylamine and neryldiethylamine. Boiling point, 83-85° C./400 Pa. Neryldiethylamine A solution prepared was introduced into a 100-ml pressure tube in a nitrogen atmosphere prepared at 90° C. for 2.5 hours To the resultant reaction mixture After liquid separation the organic layer was separated distilled to recover the unreacted isoprene was distilled under reduced pressure to obtain

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

実験手順: A solution prepared by mixing 2.93 g (40.0 mmol) of diethylamine with 18.0 ml (180 mmol) of isoprene was introduced into a 100-ml pressure tube in a nitrogen atmosphere. Thereto was gradually added dropwise at 0° C. a solution (1.6 M solution) prepared by dissolving 0.064 g of n-butyllithium (1.0 mmol) in 0.63 ml of hexane. This mixture was stirred first at room temperature for 15 minutes and then at 90° C. for 2.5 hours. To the resultant reaction mixture was added 0.3 ml of water to deactivate the catalyst. After liquid separation, the organic layer was separated and distilled to recover the unreacted isoprene. Subsequently, the concentrate remaining after the isoprene recovery was distilled under reduced pressure to obtain 7.29 g (34.8 mmol; GC yield, 87.0%) of the target mixture comprising α-neryldiethylamine and neryldiethylamine. Boiling point, 83-85° C./400 Pa. Neryldiethylamine A solution prepared was introduced into a 100-ml pressure tube in a nitrogen atmosphere prepared at 90° C. for 2.5 hours To the resultant reaction mixture After liquid separation the organic layer was separated distilled to recover the unreacted isoprene was distilled under reduced pressure to obtain

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

実験手順: A solution prepared by mixing 2.93 g (40.0 mmol) of diethylamine with 18.0 ml (180 mmol) of isoprene was introduced into a 100-ml pressure tube in a nitrogen atmosphere- Thereto was gradually added dropwise at 0° C. a solution (1.6 M solution) prepared by dissolving 0.064 g of n-butyllithium (1.0 mmol) in 0.63 ml of hexane. This mixture was stirred first at room temperature for 15 minutes and then at 90° C. for 2.5 hours. To the resultant reaction mixture was added 0.3 ml of water to deactivate the catalyst. After liquid separation, the organic layer was separated and distilled to recover the unreacted isoprene. Subsequently, the concentrate remaining after the isoprene recovery was distilled under reduced pressure to obtain 7.29 g (34.8 mmol; GC yield, 87.0%) of the target mixture comprising α-neryldiethylamine and neryldiethylamine. A solution prepared was introduced into a 100-ml pressure tube in a nitrogen prepared at 90° C. for 2.5 hours To the resultant reaction mixture After liquid separation the organic layer was separated distilled to recover the unreacted isoprene was distilled under reduced pressure to obtain

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

実験手順: 1.14 g (5.0 mmol) of (Z)-N,N-diethyl-3,7-dimethyl-2,6-octadienylamine, 5 ml of tetrahydrofuran and 16 mg (0.0192 mmol) of [η4 -bicyclo[2.2.1]hepta-2,5-diene][(R)-(6,6'-dimethyl-2,2'-biphenylylene)-bis(diphenylphosphine)]rhodium (I) tetrafluoroborate were placed in a Pyrex bomb tube under nitrogen. After degasifying the mixture, the tube was sealed and heated in a bomb tube oven at 85° C. to 90° C. for 19 hours. The brownish-red mixture was evaporated and the residue was distilled in a bulb-tube at about 120° C./0.05 mmHg. There were obtained 1.09 g of (1E,3R)-N,N-diethyl-3,7-dimethyl-1,6-octadienylamine as a colourless distillate. the tube was sealed heated in a bomb tube oven at 85° C. to 90° C. for 19 hours The brownish-red mixture was evaporated the residue was distilled in a bulb-tube at about 120° C./0.05 mmHg

反応条件: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 11.37 g (50 mmol) of (Z)-N,N-diethyl-3,7-dimethyl-2,6-octadienylamine, 101.5 mg (0.25 mmol) of bis[η4 -(Z,Z)-1,5-cyclooctadiene]rhodium(I) tetrafluoroborate, 160 mg (0.275 mmol) of (R)-(6,6'-dimethoxybiphenyl-2,2'-diyl)bis(diphenylphosphine) and 25 ml of tetrahydrofuran was heated to 65° C. while stirring for 20 hours. The brownish-red reaction mixture was evaporated and the residue was distilled in a bulb-tube at about 150° C./0.2 mbar, whereby 10.7 g of (1E,3R)-N,N-diethyl-3,7-dimethyl-1,6-octadienylamine were obtained as a light yellowish oil. The distillate was diluted with 20 ml of hexane, treated with 50 ml of 50% acetic acid and the two-phase mixture was stirred vigorously for 1 hour. After working-up in an analogous manner to Example 14 and distillation in a bulb-tube at 140° C./15 mbar there were obtained 7.18 g of (R)-citronellal as a colourless liquid: e.e=98.6% The brownish-red reaction mixture was evaporated the residue was distilled in a bulb-tube at about 150° C./0.2 mbar