ethyl 2-methylhex-4-ynoate

反応条件: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Under argon atmosphere, a solution of n-butyl lithium in hexane (1.64N, 26 ml, 0.043 mol) was dropwise added with stirring into a solution of anhydrous diisopropylamine (4.3 g, 0.043 mol) in anhydrous THF (35 ml) at -20° C. and the reaction mixture was stirred for 30 min. at -20° C. To the mixture was added dropwise a solution of ethyl 2-methyl-4-hexynoate (5.4 g, 0.035 mol) in anhydrous THF (15 ml) at -20° C. To the mixture was added anhydrous HMPA (2.25 ml, 0.013 mol). The reaction mixture was heated to room temperature and then stirred for 40 min. The mixture was again cooled to -30° C. and to the mixture was dropwise added a solution of methyl iodide (6.05 g, 0.043 mol) in anhydrous THF (5 ml). After warming to room temperature, the mixture was stirred for one hour, acetic acid (2.5 ml, 0.043 mol) was added, and the resulting mixture was concentrated. The residue was diluted with water (50 ml) and extracted with ethyl acetate (100 ml×2). The combined ethyl acetate layer were washed with water (30 ml) and with brine (20 ml), dried over anhydrous sodium sulfate, and concentrated. Distillation of the residue in vacuo give ethyl 2,2-dimethyl-4-hexynoate (3.7 g, 0.022 mol, 62%, B.p.: 65°-68° C./10 mmHg). The product was assigned the structure by the following data. The reaction mixture was heated to room temperature stirred for 40 min The mixture was again cooled to -30° C. and to the mixture After warming to room temperature the mixture was stirred for one hour the resulting mixture was concentrated The residue was diluted with water (50 ml) extracted with ethyl acetate (100 ml×2) The combined ethyl acetate layer were washed with water (30 ml) and with brine (20 ml) dried over anhydrous sodium sulfate concentrated Distillation of the residue in vacuo

反応条件: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Under argon atmosphere, a solution of n-butyl lithium in hexane (1.64N, 26 ml, 0.043 mol) was dropwise added with stirring into a solution of anhydrous diisopropylamine (4.3 g, 0.043 mol) in anhydrous THF (35 ml) at -20° C. and the reaction mixture was stirred for 30 min. at -20° C. To the mixture was added dropwise a solution of ethyl 2-methyl-4-hexynoate (5.4 g, 0.035 mol) in anhydrous THF (15 ml) at -20° C. To the mixture was added anhydrous HMPA (2.25 ml, 0.013 mol). The reaction mixture was heated to room temperature and then stirred for 40 min. The mixture was again cooled to -30° C. and to the mixture was dropwise added a solution of methyl iodide (6.05 g, 0.043 mol) in anhydrous THF (5 ml). After warming to room temperature, the mixture was stirred for one hour, acetic acid (2.5 ml, 0.043 mol) was added, and the resulting mixture was concentrated. The residue was diluted with water (50 ml) and extracted with ethyl acetate (100 ml×2). The combined ethyl acetate layer were washed with water (30 ml) and with brine (20 ml), dried over anhydrous sodium sulfate, and concentrated. Distillation of the residue in vacuo give ethyl 2,2-dimethyl-4-hexynoate (3.7 g, 0.022 mol, 62%, B.p.: 65°-68° C./10 mmHg). The product was assigned the structure by the following data. The reaction mixture was heated to room temperature stirred for 40 min The mixture was again cooled to -30° C. and to the mixture After warming to room temperature the mixture was stirred for one hour the resulting mixture was concentrated The residue was diluted with water (50 ml) extracted with ethyl acetate (100 ml×2) The combined ethyl acetate layer were washed with water (30 ml) and with brine (20 ml) dried over anhydrous sodium sulfate concentrated Distillation of the residue in vacuo

反応条件: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Under argon atmosphere, a solution of n-butyl lithium in hexane (1.64N, 26 ml, 0.043 mol) was dropwise added with stirring into a solution of anhydrous diisopropylamine (4.3 g, 0.043 mol) in anhydrous THF (35 ml) at -20° C. and the reaction mixture was stirred for 30 min. at -20° C. To the mixture was added dropwise a solution of ethyl 2-methyl-4-hexynoate (5.4 g, 0.035 mol) in anhydrous THF (15 ml) at -20° C. To the mixture was added anhydrous HMPA (2.25 ml, 0.013 mol). The reaction mixture was heated to room temperature and then stirred for 40 min. The mixture was again cooled to -30° C. and to the mixture was dropwise added a solution of methyl iodide (6.05 g, 0.043 mol) in anhydrous THF (5 ml). After warming to room temperature, the mixture was stirred for one hour, acetic acid (2.5 ml, 0.043 mol) was added, and the resulting mixture was concentrated. The residue was diluted with water (50 ml) and extracted with ethyl acetate (100 ml×2). The combined ethyl acetate layer were washed with water (30 ml) and with brine (20 ml), dried over anhydrous sodium sulfate, and concentrated. Distillation of the residue in vacuo give ethyl 2,2-dimethyl-4-hexynoate (3.7 g, 0.022 mol, 62%, B.p.: 65°-68° C./10 mmHg). The product was assigned the structure by the following data. The reaction mixture was heated to room temperature stirred for 40 min The mixture was again cooled to -30° C. and to the mixture After warming to room temperature the mixture was stirred for one hour the resulting mixture was concentrated The residue was diluted with water (50 ml) extracted with ethyl acetate (100 ml×2) The combined ethyl acetate layer were washed with water (30 ml) and with brine (20 ml) dried over anhydrous sodium sulfate concentrated Distillation of the residue in vacuo