1-trimethylsilylazepan-2-one

反応条件: temp:0.00; pressure:0.00; stir:

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: Hexahydro-1-trimethylsilyl-2H-azepin-2-one (9.2 g) in dry tetrahydrofuran (20 ml) was added dropwise with cooling and stirring under a nitrogen atmosphere to a solution of lithium-2,2,6,6-tetramethylpiperidide (prepared from 2,2,6,6-tetramethylpiperidine (8.48 g) and butyl lithium (0.06 mole) in hexane-tetrahydrofuran (38 ml; 10 ml). A further portion of butyl lithium (0.06 mole) in hexane (38 ml) was then added, followed by o-chloroanisole (8.54 g) keeping the reaction temperature between -10° and 5° C. After allowing to warm to room temperature the reaction was stirred for 1.5 hours then decomposed by the addition of water (100 ml). The solvents were removed under reduced pressure, the resulting product partitioned between toluene and 5 M hydrochloric acid. The toluene extracts were dried (MgSO4), the solvent removed and the product distilled affording 2.7 g b.p. 160°-170° C. at 0.1 mm, which yielded 2.6 g of the crystalline title compound from ethyl acetate. with cooling the reaction temperature between -10° and 5° C The solvents were removed under reduced pressure the resulting product partitioned between toluene and 5 M hydrochloric acid The toluene extracts were dried (MgSO4) the solvent removed the product distilled affording 2.7 g b.p. 160°-170° C. at 0.1 mm, which

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

実験手順: To 1.6 M n-BuLi in hexane (31.3 mL, 50 mmol) at 0° C. was added a solution of 2,2,6,6-tetramethyl piperidine (8.43 mL, 50 mmol) in anhydrous THF (100 mL) over 5 min. 1-Trimethylsilanyl-azepan-2-one (as described in Step F above) (9.26 g, 50 mmol) in anhydrous THF (20 mL) was added. After stirring the reaction mixture for 10 min, a further portion of 1.6M n-BuLi in hexane (31.3 mL, 50 mmol) was added, the mixture stirred for 10 min, and 2-chloroanisole (6.34 mL, 50 mmol) was added. After stirring for 30 min under Ar, ethyl iodide (3.90 mL, 48.7 mmol) was added, the reaction mixture was stirred for 30 min, quenched with H2O, concentrated in vacuo, diluted with EtOAc, and washed with 5N HCl (100 mL) and brine. The organic layer was dried (MgSO4), concentrated and purified using SiO2 chromatography (10-15% EtOAc/CH2Cl2) to give the title compound the mixture stirred for 10 min was added the reaction mixture was stirred for 30 min quenched with H2O concentrated in vacuo diluted with EtOAc washed with 5N HCl (100 mL) and brine The organic layer was dried (MgSO4) concentrated purified

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

実験手順: To 1.6 M n-BuLi in hexane (31.3 mL, 50 mmol) at 0° C. was added a solution of 2,2,6,6-tetramethyl piperidine (8.43 mL, 50 mmol) in anhydrous THF (100 mL) over 5 min. 1-Trimethylsilanyl-azepan-2-one (as described in Step F above) (9.26 g, 50 mmol) in anhydrous THF (20 mL) was added. After stirring the reaction mixture for 10 min a further portion of 1.6M n-BuLi in hexane (31.3 mL, 50 mmol) was added, the mixture stirred for 10 min, and 2-chloroanisole (6.34 mL, 50 mmol) was added. After stirring for 30 min under Ar, the reaction was quenched with H2O, stirred for 30 min, concentrated in vacuo, diluted with EtOAc, washed with 5N HCl (100 mL) and brine. The organic layer was dried (MgSO4), concentrated and purified using SiO2 chromatography (0.5% MeOH/CH2Cl2) to give the title compound. was added After stirring for 30 min under Ar the reaction was quenched with H2O stirred for 30 min concentrated in vacuo diluted with EtOAc washed with 5N HCl (100 mL) and brine The organic layer was dried (MgSO4) concentrated purified

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

実験手順: To 1.6 M n-BuLi in hexane (31.3 mL, 50 mmol) at 0° C. was added a solution of 2,2,6,6-tetramethyl piperidine (8.43 mL, 50 mmol) in anhydrous THF (100 mL) over 5 min. 1-Trimethylsilanyl-azepan-2-one (as described in Step F above) (9.26 g, 50 mmol) in anhydrous THF (20 mL) was added. After stirring the reaction mixture for 10 min a further portion of 1.6M n-BuLi in hexane (31.3 mL, 50 mmol) was added, the mixture stirred for 10 min, and 2-chloroanisole (6.34 mL, 50 mmol) was added. After stirring for 30 min under Ar, the reaction was quenched with H2O, stirred for 30 min, concentrated in vacuo, diluted with EtOAc, washed with 5N HCl (100 mL) and brine. The organic layer was dried (MgSO4), concentrated and purified using SiO2 chromatography (0.5% MeOH/CH2Cl2) to give the title compound. was added After stirring for 30 min under Ar the reaction was quenched with H2O stirred for 30 min concentrated in vacuo diluted with EtOAc washed with 5N HCl (100 mL) and brine The organic layer was dried (MgSO4) concentrated purified

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

実験手順: Caprolactam, which is commercially available, (10.0 g, 88.0 mmol), Et3N (14.8 mL, 106 mmol) and chlorotrimethylsilane (13.5 mL, 106 mmol) were dissolved in toluene (60 mL) and refluxed under Ar for 3 h. The reaction was filtered and concentrated to give the title compound. refluxed under Ar for 3 h The reaction was filtered concentrated

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: 5.4 g (0.1 mol) of sodium methylate and 18.5 g (0.1 mol) of N-trimethylsilylcaprolactam are introduced successively into 150 ml of 1,2-dimethoxyethane, and the mixture is stirred at room temperature for 30 minutes. Then 11 g (0.1 mol) of methyl methanesulfonate are added dropwise. After the reaction mixture has been stirred at 50° C. for a further one hour, it is cooled, the sodium mesylate is removed by filtration with suction, and the filtrate is evaporated. The oily residue is distilled in vacuo. After the reaction mixture has been stirred at 50° C. for a further one hour it is cooled the sodium mesylate is removed by filtration with suction the filtrate is evaporated The oily residue is distilled in vacuo

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

実験手順: 5.4 g (0.1 mol) of sodium methylate and 18.5 g (0.1 mol) of N-trimethylsilylcaprolactam are introduced successively into 150 ml of 1,2-dimethoxyethane, and the mixture is stirred at room temperature for 30 minutes. Then 11 g (0.1 mol) of methyl methanesulfonate are added dropwise. After the reaction mixture has been stirred at 50° C. for a further one hour, it is cooled, the sodium mesylate is removed by filtration with suction, and the filtrate is evaporated. The oily residue is distilled in vacuo. After the reaction mixture has been stirred at 50° C. for a further one hour it is cooled the sodium mesylate is removed by filtration with suction the filtrate is evaporated The oily residue is distilled in vacuo

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

実験手順: 5.4 g (0.1 mol) of sodium methylate and 18.5 g (0.1 mol) of N-trimethylsilylcaprolactam are introduced successively into 150 ml of 1,2-dimethoxyethane, and the mixture is stirred at room temperature for 30 minutes. Then 11 g (0.1 mol) of methyl methanesulfonate are added dropwise. After the reaction mixture has been stirred at 50° C. for a further one hour, it is cooled, the sodium mesylate is removed by filtration with suction, and the filtrate is evaporated. The oily residue is distilled in vacuo. After the reaction mixture has been stirred at 50° C. for a further one hour it is cooled the sodium mesylate is removed by filtration with suction the filtrate is evaporated The oily residue is distilled in vacuo

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

実験手順: 3.1 g (0.05 mol) of sodium oxide (Na2O) are suspended in 150 ml of 1,2-dimethoxyethane, and then 18.5 g (0.1 mol) of N-trimethylsilylcaprolactam are added. The reaction mixture is stirred at 50° C. for two hours, during which the voluminous precipitate of the sodium salt of the caprolactam forms. Then 24.9 g (0.1 mol) of n-dodecyl bromide are added, and the mixture is stirred and heated under reflux for 20 hours. The working-up is carried out as indicated in Example 1. heated under reflux for 20 hours