cycloheptanecarbonitrile

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: Obtained by operating as in example 27b, from 195 mmoles of lithiated diisopropylamine (25.6 g (252.9 mmoles) of diisopropylamine treated with 122 ml (195 mmoles) of n-butyllithium 1.6M in hexane) in 300 ml of dry tetrahydrofuran, 24 g (195 mmoles) of commercial cycloheptanecarbonitrile and 24.6 g (195 mmoles) of benzyl chloride. After distillation, there is obtained 23.2 g (yield=55.8%) of a yellow viscous liquid. b.p.16 =190°-7° C. Obtained After distillation

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

実験手順: Obtained by operating as in example 27b, from 195 mmoles of lithiated diisopropylamine (25.6 g (252.9 mmoles) of diisopropylamine treated with 122 ml (195 mmoles) of n-butyllithium 1.6M in hexane) in 300 ml of dry tetrahydrofuran, 24 g (195 mmoles) of commercial cycloheptanecarbonitrile and 24.6 g (195 mmoles) of benzyl chloride. After distillation, there is obtained 23.2 g (yield=55.8%) of a yellow viscous liquid. b.p.16 =190°-7° C. Obtained After distillation

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

実験手順: A solution of cycloheptanecarbonitrile (12.3 g), 100 mmol) in THF (50 ml) was added dropwise to a well stirred solution of lithium diisopropylamide (105 mmol) in THF/hexane (75 ml/60 ml) under nitrogen, keeping the temperature at -65°. After 1 h, the solution was allowed to warm to ambient temperature and added dropwise to a well stirred solution of bromochloromethane (32.5 ml; 500 mmol) in THF (50 ml) under nitrogen keeping the temperature between -50° and -60°. After 10 min, the solution was allowed to warm to ambient temperature, poured into water (250 ml) and the aqueous mixture extracted with chloroform (3×150 ml). The extracts were washed with 2N-HCl (2×50 ml), saturated aq. NaHCO3 (100 ml), and water (100 ml), then dried (MgSO4) and evaporated under reduced pressure to give a brown oil (18.0 g). Distillation gave the title compound (12.65 g), b.p. 78°-80° at 0.25 mmHg. at -65° added dropwise to a well After 10 min to warm to ambient temperature the aqueous mixture extracted with chloroform (3×150 ml) The extracts were washed with 2N-HCl (2×50 ml), saturated aq. NaHCO3 (100 ml), and water (100 ml) dried (MgSO4) evaporated under reduced pressure

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

実験手順: Obtained by operating as in example 27b, from 195 mmoles of lithiated diisopropylamine (25.6 g (252.9 mmoles) of diisopropylamine treated with 122 ml (195 mmoles) of n-butyllithium 1.6M in hexane) in 300 ml of dry tetrahydrofuran, 24 g (195 mmoles) of commercial cycloheptanecarbonitrile and 24.6 g (195 mmoles) of benzyl chloride. After distillation, there is obtained 23.2 g (yield=55.8%) of a yellow viscous liquid. b.p.16 =190°-7° C. Obtained After distillation

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: Obtained by operating as in example 27b, from 195 mmoles of lithiated diisopropylamine (25.6 g (252.9 mmoles) of diisopropylamine treated with 122 ml (195 mmoles) of n-butyllithium 1.6M in hexane) in 300 ml of dry tetrahydrofuran, 24 g (195 mmoles) of commercial cycloheptanecarbonitrile and 24.6 g (195 mmoles) of benzyl chloride. After distillation, there is obtained 23.2 g (yield=55.8%) of a yellow viscous liquid. b.p.16 =190°-7° C. Obtained After distillation

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

実験手順: Phenylmagnesium bromide (3.0M solution in diethyl ether) (271 mL), was added dropwise to a stirred (overhead stirrer) solution of cycloheptanecarbonitrile (50 g) in 229 mL diethyl ether under nitrogen at such a rate as to maintain gentle reflux. The reaction mixture was then heated at reflux for 3 hours. TLC indicated no starting material present in the reaction mixture. The reaction mixture was allowed to cool to room temperature and stood under nitrogen overnight. The reaction mixture was cooled to 0° C. and treated dropwise with 102 mL 4N HCl(aq) keeping the temperature below 20° C. 4N sulfuric acid (203 mL) was added dropwise rapidly to start with and then more slowly towards the end. The ice bath was removed and the diethyl ether was distilled off. The reaction mixture was heated at 80-90° C. for 3.5 hours then allowed to cool to room temperature and stood overnight. The mixture was diluted with ether (approx 450 mL) and water (100 mL). The layers were separated and the aqueous layer was extracted with ether (2×400 mL). The organic layers were combined and washed with saturated aqueous sodium hydrogen carbonate (600 mL) and brine (600 mL), dried over magnesium sulphate, filtered and evaporated to give the sub-titled compound as an orange liquid (86.5 g). to maintain gentle reflux The reaction mixture was then heated at reflux for 3 hours The reaction mixture was cooled to 0° C. the temperature below 20° C The ice bath was removed the diethyl ether was distilled off The reaction mixture was heated at 80-90° C. for 3.5 hours to cool to room temperature stood overnight The mixture was diluted with ether (approx 450 mL) and water (100 mL) The layers were separated the aqueous layer was extracted with ether (2×400 mL) washed with saturated aqueous sodium hydrogen carbonate (600 mL) and brine (600 mL) dried over magnesium sulphate filtered evaporated

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

実験手順: A solution of cycloheptanecarbonitrile (12.3 g), 100 mmol) in THF (50 ml) was added dropwise to a well stirred solution of lithium diisopropylamide (105 mmol) in THF/hexane (75 ml/60 ml) under nitrogen, keeping the temperature at -65°. After 1 h, the solution was allowed to warm to ambient temperature and added dropwise to a well stirred solution of bromochloromethane (32.5 ml; 500 mmol) in THF (50 ml) under nitrogen keeping the temperature between -50° and -60°. After 10 min, the solution was allowed to warm to ambient temperature, poured into water (250 ml) and the aqueous mixture extracted with chloroform (3×150 ml). The extracts were washed with 2N-HCl (2×50 ml), saturated aq. NaHCO3 (100 ml), and water (100 ml), then dried (MgSO4) and evaporated under reduced pressure to give a brown oil (18.0 g). Distillation gave the title compound (12.65 g), b.p. 78°-80° at 0.25 mmHg. at -65° added dropwise to a well After 10 min to warm to ambient temperature the aqueous mixture extracted with chloroform (3×150 ml) The extracts were washed with 2N-HCl (2×50 ml), saturated aq. NaHCO3 (100 ml), and water (100 ml) dried (MgSO4) evaporated under reduced pressure

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

実験手順: Obtained by operating as in example 27b, from 195 mmoles of lithiated diisopropylamine (25.6 g (252.9 mmoles) of diisopropylamine treated with 122 ml (195 mmoles) of n-butyllithium 1.6M in hexane) in 300 ml of dry tetrahydrofuran, 24 g (195 mmoles) of commercial cycloheptanecarbonitrile and 24.6 g (195 mmoles) of benzyl chloride. After distillation, there is obtained 23.2 g (yield=55.8%) of a yellow viscous liquid. b.p.16 =190°-7° C. Obtained After distillation