tert-butyl 2,2-dichloroacetate

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:-30.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 12.3 g of cyclopentylmethyl ketone and 18.5 g of tert.-butyl dichloroacetate was cooled to -30° C with stirring under an inert atmosphere and a solution of 12.2 g of potassium tert.-butylate in 60 ml of tetrahydrofuran was added thereto at the said temperature. After returning to room temperature, hexane and water were added and the organic phase was separated, washed with water and dried over magnesium sulfate. The solvents were evaporated off to leave an oily residue of tert.-butyl 2-chloro-3-cyclopentyl-2,3-epoxy-butanoate. 26.5 g of the latter product was added to a solution of 3 g of lithium carbonate and 20 g of lithium bromide in 100 ml of hexamethylphosphorotriamide and after stirring for 1 hour at room temperature, petroleum ether and water were added thereto. The organic phase was washed with water, dried over magnesium sulfate and filtered. The solvent was evaporated to obtain an oily residue which was tert.-butyl 3-cyclopentyl-2-oxo-3-butenoate which was used as is for the next step. After returning to room temperature the organic phase was separated washed with water dried over magnesium sulfate The solvents were evaporated off

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

実験手順: A solution of 122 g of potassium tert.-butylate in 720 ml of tetrahydrofuran was added at -20° C. with stirring under an inert atmosphere to a mixture of 95 g of methyl isopropyl ketone and 185 g of tert.butyl dichloroacetate and after returning the temperature to room temperature, the mixture was stirred for 2 hours. The mixture was poured into ice water and the mixture was stirred and the organic phase was separated. The organic phase was washed with aqueous sodium chloride solution, dried over magnesium sulfate, passed through vegetable charcoal and concentrated to dryness to obtain 230.4 g of tert.butyl 2-chloro-2,3-epoxy-3-isopropyl-butanoate. to room temperature the mixture was stirred the organic phase was separated The organic phase was washed with aqueous sodium chloride solution dried over magnesium sulfate concentrated to dryness

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

実験手順: A solution of 122 g of potassium tert.-butylate in 720 ml of tetrahydrofuran was added at -20° C. with stirring under an inert atmosphere to a mixture of 95 g of methyl isopropyl ketone and 185 g of tert.butyl dichloroacetate and after returning the temperature to room temperature, the mixture was stirred for 2 hours. The mixture was poured into ice water and the mixture was stirred and the organic phase was separated. The organic phase was washed with aqueous sodium chloride solution, dried over magnesium sulfate, passed through vegetable charcoal and concentrated to dryness to obtain 230.4 g of tert.butyl 2-chloro-2,3-epoxy-3-isopropyl-butanoate. to room temperature the mixture was stirred the organic phase was separated The organic phase was washed with aqueous sodium chloride solution dried over magnesium sulfate concentrated to dryness

反応条件: temp:-30.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 12.3 g of cyclopentylmethyl ketone and 18.5 g of tert.-butyl dichloroacetate was cooled to -30° C with stirring under an inert atmosphere and a solution of 12.2 g of potassium tert.-butylate in 60 ml of tetrahydrofuran was added thereto at the said temperature. After returning to room temperature, hexane and water were added and the organic phase was separated, washed with water and dried over magnesium sulfate. The solvents were evaporated off to leave an oily residue of tert.-butyl 2-chloro-3-cyclopentyl-2,3-epoxy-butanoate. 26.5 g of the latter product was added to a solution of 3 g of lithium carbonate and 20 g of lithium bromide in 100 ml of hexamethylphosphorotriamide and after stirring for 1 hour at room temperature, petroleum ether and water were added thereto. The organic phase was washed with water, dried over magnesium sulfate and filtered. The solvent was evaporated to obtain an oily residue which was tert.-butyl 3-cyclopentyl-2-oxo-3-butenoate which was used as is for the next step. After returning to room temperature the organic phase was separated washed with water dried over magnesium sulfate The solvents were evaporated off

反応条件: temp:-30.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 12.3 g of cyclopentylmethyl ketone and 18.5 g of tert.-butyl dichloroacetate was cooled to -30° C with stirring under an inert atmosphere and a solution of 12.2 g of potassium tert.-butylate in 60 ml of tetrahydrofuran was added thereto at the said temperature. After returning to room temperature, hexane and water were added and the organic phase was separated, washed with water and dried over magnesium sulfate. The solvents were evaporated off to leave an oily residue of tert.-butyl 2-chloro-3-cyclopentyl-2,3-epoxy-butanoate. 26.5 g of the latter product was added to a solution of 3 g of lithium carbonate and 20 g of lithium bromide in 100 ml of hexamethylphosphorotriamide and after stirring for 1 hour at room temperature, petroleum ether and water were added thereto. The organic phase was washed with water, dried over magnesium sulfate and filtered. The solvent was evaporated to obtain an oily residue which was tert.-butyl 3-cyclopentyl-2-oxo-3-butenoate which was used as is for the next step. After returning to room temperature the organic phase was separated washed with water dried over magnesium sulfate The solvents were evaporated off

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:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 2.106 g of methoxyacetaldehyde, 3.8 ml of tertbutyl dichloroacetate and 25 ml of tetrahydrofuran was cooled to -20° C. and over 15 minutes, 29 ml of potassium tertbutylate in tetrahydrofuran (0.9M) were introduced. The mixture stood for 20 minutes and 25 ml of ether and 25 ml of water were added. The mixture was extracted with ether and the organic phase was washed with water saturated with sodium chloride, then dried and concentrated to dryness under reduced pressure. The residue was chromatographed over silica and eluted with methylene chloride to obtain 1.44 g of 1,1-dimethylethyl 2-chloro-3-methoxymethyloxirane-carboxylate. The mixture was extracted with ether the organic phase was washed with water saturated with sodium chloride dried concentrated to dryness under reduced pressure The residue was chromatographed over silica eluted with methylene chloride

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

実験手順: A mixture of 2.106 g of methoxyacetaldehyde, 3.8 ml of tertbutyl dichloroacetate and 25 ml of tetrahydrofuran was cooled to -20° C. and over 15 minutes, 29 ml of potassium tertbutylate in tetrahydrofuran (0.9M) were introduced. The mixture stood for 20 minutes and 25 ml of ether and 25 ml of water were added. The mixture was extracted with ether and the organic phase was washed with water saturated with sodium chloride, then dried and concentrated to dryness under reduced pressure. The residue was chromatographed over silica and eluted with methylene chloride to obtain 1.44 g of 1,1-dimethylethyl 2-chloro-3-methoxymethyloxirane-carboxylate. The mixture was extracted with ether the organic phase was washed with water saturated with sodium chloride dried concentrated to dryness under reduced pressure The residue was chromatographed over silica eluted with methylene chloride

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

実験手順: A mixture of 2.106 g of methoxyacetaldehyde, 3.8 ml of tertbutyl dichloroacetate and 25 ml of tetrahydrofuran was cooled to -20° C. and over 15 minutes, 29 ml of potassium tertbutylate in tetrahydrofuran (0.9M) were introduced. The mixture stood for 20 minutes and 25 ml of ether and 25 ml of water were added. The mixture was extracted with ether and the organic phase was washed with water saturated with sodium chloride, then dried and concentrated to dryness under reduced pressure. The residue was chromatographed over silica and eluted with methylene chloride to obtain 1.44 g of 1,1-dimethylethyl 2-chloro-3-methoxymethyloxirane-carboxylate. The mixture was extracted with ether the organic phase was washed with water saturated with sodium chloride dried concentrated to dryness under reduced pressure The residue was chromatographed over silica eluted with methylene chloride