3-ethyl-1-methylazepan-2-one

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

実験手順: 2,2,6,6-tetramethylpiperidine (8.48 g) was added dropwise with cooling and stirring under nitrogen to a solution of butyl lithium (0.05 mole) in hexane (31.25 ml) and tetrahydrofuran (15 ml). 3-Ethylhexahydro-1-methyl-2H-azepin-2-one (7.75 g) in dry tetrahydrofuran (20 ml) was added. On completion of this addition a further portion of butyl lithium (0.06 mole) in hexane (37.5 ml) was added with cooling. After ten minutes o-chloroanisole (8.54 g) was added dropwise in tetrahydrofuran (20 ml). The reaction was then stirred at ambient temperature for c.a. 20 hours. The reaction mixture was poured into water, and the tetrahydrofuran removed under reduced pressure. After acidifying with 5 M hydrochloric acid the mixture was extracted with toluene. Toluene extracts were washed with water, dried (MgSO4) and after removal of the solvent the product distilled affording 2.37 g, b.p. 150°-170° C. at 0.6 mm. Corrected by purity by g.l.c. assay, the yield of the title compound was 15.8%. with cooling was added with cooling 20 hours the tetrahydrofuran removed under reduced pressure was extracted with toluene Toluene extracts were washed with water dried (MgSO4) after removal of the solvent the product distilled affording 2.37 g, b.p. 150°-170° C. at 0.6 mm

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

実験手順: 2,2,6,6-tetramethylpiperidine (8.48 g) was added dropwise with cooling and stirring under nitrogen to a solution of butyl lithium (0.05 mole) in hexane (31.25 ml) and tetrahydrofuran (15 ml). 3-Ethylhexahydro-1-methyl-2H-azepin-2-one (7.75 g) in dry tetrahydrofuran (20 ml) was added. On completion of this addition a further portion of butyl lithium (0.06 mole) in hexane (37.5 ml) was added with cooling. After ten minutes o-chloroanisole (8.54 g) was added dropwise in tetrahydrofuran (20 ml). The reaction was then stirred at ambient temperature for c.a. 20 hours. The reaction mixture was poured into water, and the tetrahydrofuran removed under reduced pressure. After acidifying with 5 M hydrochloric acid the mixture was extracted with toluene. Toluene extracts were washed with water, dried (MgSO4) and after removal of the solvent the product distilled affording 2.37 g, b.p. 150°-170° C. at 0.6 mm. Corrected by purity by g.l.c. assay, the yield of the title compound was 15.8%. with cooling was added with cooling 20 hours the tetrahydrofuran removed under reduced pressure was extracted with toluene Toluene extracts were washed with water dried (MgSO4) after removal of the solvent the product distilled affording 2.37 g, b.p. 150°-170° C. at 0.6 mm

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

実験手順: A 2 molar solution of isopropylmagnesium bromide in ether (70 ml) was treated with 3-ethyl-hexahydro-1-methyl-2H-azepin-2-one (21.7 g, Aust. J. Chem. 1976, 29 2651) in THF (20 ml) and the mixture treated dropwise with diisopropylamine (19.6 ml) (exothermic). The reaction mixture was stirred for 2 hours then treated dropwise with 3-methoxy-2-cyclohexenone (12.6 g) in THF (20 ml). After stirring for 2 hours the reaction mixture was poured onto cold 2 N HCl (250 ml). After 10 minutes the mixture was extracted with dichloromethane (2×300 ml), the combined organic phases washed with saturated aqueous NaHCO3 solution and dried (MgSO4). Removal of the solvents under reduced pressure followed by distillation gave the title compound as a viscous oil (Bpt 155°-160° C./0.1 mm) (13 g). Redistillation (154°-158° C./0.07 mm) gave analytically pure material. After stirring for 2 hours the reaction mixture After 10 minutes the mixture was extracted with dichloromethane (2×300 ml) the combined organic phases washed with saturated aqueous NaHCO3 solution dried (MgSO4) Removal of the solvents under reduced pressure followed by distillation

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

実験手順: 2,2,6,6-tetramethylpiperidine (8.48 g) was added dropwise with cooling and stirring under nitrogen to a solution of butyl lithium (0.05 mole) in hexane (31.25 ml) and tetrahydrofuran (15 ml). 3-Ethylhexahydro-1-methyl-2H-azepin-2-one (7.75 g) in dry tetrahydrofuran (20 ml) was added. On completion of this addition a further portion of butyl lithium (0.06 mole) in hexane (37.5 ml) was added with cooling. After ten minutes o-chloroanisole (8.54 g) was added dropwise in tetrahydrofuran (20 ml). The reaction was then stirred at ambient temperature for c.a. 20 hours. The reaction mixture was poured into water, and the tetrahydrofuran removed under reduced pressure. After acidifying with 5 M hydrochloric acid the mixture was extracted with toluene. Toluene extracts were washed with water, dried (MgSO4) and after removal of the solvent the product distilled affording 2.37 g, b.p. 150°-170° C. at 0.6 mm. Corrected by purity by g.l.c. assay, the yield of the title compound was 15.8%. with cooling was added with cooling 20 hours the tetrahydrofuran removed under reduced pressure was extracted with toluene Toluene extracts were washed with water dried (MgSO4) after removal of the solvent the product distilled affording 2.37 g, b.p. 150°-170° C. at 0.6 mm