4-fluoro-3,3-dimethylbutan-2-one

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

実験手順: 4.18 kg (35.4 mol) of 1-fluoro-2,2-dimethyl-butan-3-one were dissolved in 30 liters of methylene chloride, and 5.67 kg of bromine were added dropwise at 20° C. in the course of 2 hours such that continuous decolorisation occurred. The solvent was distilled off under a waterpump vacuum, a further 15 liters of methylene chloride were added to the residue and the solvent was again distilled off under a waterpump vacuum. The crude 1-fluoro-4-bromo-2,2-dimethyl-butan-3-one (6.97 kg, quantitative yield) was added dropwise to 2.45 kg of 1,2,4-triazole and 4.89 kg of potassium carbonate in 21.4 liters of acetone at 30° to 35° C. in the course of 2 hours, whilst cooling. The mixture was subsequently stirred at room temperature for 15 hours, the insoluble material was filtered off and the solvent was distilled off from the filtrate under a waterpump vacuum. 6.12 kg (93% of theory) of 1-fluoro-2,2-dimethyl-4-(1,2,4-triazol-1-yl)-butan-3-one, which could be further reacted directly, were obtained. The solvent was distilled off under a waterpump vacuum a further 15 liters of methylene chloride were added to the residue the solvent was again distilled off under a waterpump vacuum

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

実験手順: 4.18 kg (35.4 mol) of 1-fluoro-2,2-dimethyl-butan-3-one were dissolved in 30 liters of methylene chloride, and 5.67 kg of bromine were added dropwise at 20° C. in the course of 2 hours such that continuous decolorisation occurred. The solvent was distilled off under a waterpump vacuum, a further 15 liters of methylene chloride were added to the residue and the solvent was again distilled off under a waterpump vacuum. The crude 1-fluoro-4-bromo-2,2-dimethyl-butan-3-one (6.97 kg, quantitative yield) was added dropwise to 2.45 kg of 1,2,4-triazole and 4.89 kg of potassium carbonate in 21.4 liters of acetone at 30° to 35° C. in the course of 2 hours, whilst cooling. The mixture was subsequently stirred at room temperature for 15 hours, the insoluble material was filtered off and the solvent was distilled off from the filtrate under a waterpump vacuum. 6.12 kg (93% of theory) of 1-fluoro-2,2-dimethyl-4-(1,2,4-triazol-1-yl)-butan-3-one, which could be further reacted directly, were obtained. The solvent was distilled off under a waterpump vacuum a further 15 liters of methylene chloride were added to the residue the solvent was again distilled off under a waterpump vacuum

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

実験手順: 480 g of bromine were slowly added dropwise to a mixture of 354 g (3 mol) of 3,3-dimethyl-4-fluoro-butan-2-one and 2,000 ml of ether at 20° to 30° C., while cooling and stirring. The yellowish solution was subsequently stirred, at 20° C., for a further 1 hour and 500 ml of water were then added carefully. The ether phase was separated off, washed several times with water and dried over sodium sulphate. After distilling off the solvent, the residue was distilled under a waterpump vacuum. 472 g (80% theory) of 1-bromo-3,3-dimethyl-4-fluoro-butan-2-one of boiling point 80°-90° C./11 mm Hg were obtained. ##STR24## while cooling The yellowish solution was subsequently stirred, at 20° C., for a further 1 hour The ether phase was separated off washed several times with water dried over sodium sulphate After distilling off the solvent the residue was distilled under a waterpump vacuum

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

実験手順: 480 g of bromine were slowly added dropwise to a mixture of 354 g (3 mol) of 3,3-dimethyl-4-fluoro-butan-2-one and 2,000 ml of ether at 20° to 30° C., while cooling and stirring. The yellowish solution was subsequently stirred, at 20° C., for a further 1 hour and 500 ml of water were then added carefully. The ether phase was separated off, washed several times with water and dried over sodium sulphate. After distilling off the solvent, the residue was distilled under a waterpump vacuum. 472 g (80% theory) of 1-bromo-3,3-dimethyl-4-fluoro-butan-2-one of boiling point 80°-90° C./11 mm Hg were obtained. ##STR24## while cooling The yellowish solution was subsequently stirred, at 20° C., for a further 1 hour The ether phase was separated off washed several times with water dried over sodium sulphate After distilling off the solvent the residue was distilled under a waterpump vacuum

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

実験手順: To a vigorous stirring mixture of 4-fluoro-3,3-dimethylbutan-2-one (4.1 g, 34.7 mmol) in water (50 mL) and NaOH (7 mL, 70.0 mmol) cooled in an ice-acetone bath was added portionwise potassium permanganate (9.87 g, 62.5 mmol). The inner temperature was controlled between −3 to 2° C. during the addition process. Upon the completion of the addition, the reaction mixture was stirred in the ice-acetone bath for 6 hrs and then allowed to warm up. EtOH (5 mL) was added and the reaction mixture was stirred for another 15 min. The reaction mixture was filtered and the solid was washed with water (˜80 mL). The filtration was acidified with 6 N HCl, and extracted with EtOAc. The combined extracts were washed with 1N HCl, sat. NaCl, dried (Na2SO4), filtered and concentrated to yield 4-fluoro-3,3-dimethyl-2-oxobutanoic acid (2.3 g). cooled in an ice-acetone bath was controlled between −3 to 2° C. during the addition process Upon the completion of the addition to warm up The reaction mixture was filtered the solid was washed with water (˜80 mL) The filtration extracted with EtOAc The combined extracts were washed with 1N HCl, sat. NaCl dried (Na2SO4) filtered concentrated

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

実験手順: 480 g of bromine were slowly added dropwise to a mixture of 354 g (3 moles) of 3,3-dimethyl-4-fluoro-2-butanone and 2,000 ml of ether at 20° to 30° C., while cooling and stirring. The yellowish solution was subsequently stirred at 20° C. for a further hour, and 500 ml of water were then carefully added. The ether phase was separated off, washed several times with water and dried over sodium sulphate. After distilling off the solvent, the residue was distilled under a waterpump vacuum. 472 g (80% of theory) of 1-bromo-3,3-dimethyl-4-fluoro-2-butanone of boiling point 80° to 90° C./11 mm Hg column were obtained. ##STR14## while cooling The yellowish solution was subsequently stirred at 20° C. for a further hour The ether phase was separated off washed several times with water dried over sodium sulphate After distilling off the solvent the residue was distilled under a waterpump vacuum

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

実験手順: 480 g of bromine were slowly added dropwise to a mixture of 354 g (3 moles) of 3,3-dimethyl-4-fluoro-2-butanone and 2,000 ml of ether at 20° to 30° C., while cooling and stirring. The yellowish solution was subsequently stirred at 20° C. for a further hour, and 500 ml of water were then carefully added. The ether phase was separated off, washed several times with water and dried over sodium sulphate. After distilling off the solvent, the residue was distilled under a waterpump vacuum. 472 g (80% of theory) of 1-bromo-3,3-dimethyl-4-fluoro-2-butanone of boiling point 80° to 90° C./11 mm Hg column were obtained. ##STR14## while cooling The yellowish solution was subsequently stirred at 20° C. for a further hour The ether phase was separated off washed several times with water dried over sodium sulphate After distilling off the solvent the residue was distilled under a waterpump vacuum

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

実験手順: 480 g of bromine were slowly added dropwise to a mixture of 354 g (3 mol) of 3,3-dimethyl-4-fluoro-2-butanone (see Example 1) and 2000 ml of ether at 20° to 30° C., while cooling and stirring. The yellowish solution was then stirred at 20° C. for a further 1 hour, and 500 ml of water were subsequently added carefully. The ether phase was separated off, washed several times with water and dried over sodium sulphate. After distilling off the solvent, the residue was distilled under a water-pump vacuum. 472 g (80% of theory) of 1-bromo-3,3-dimethyl-4-fluoro-2-butanone of boiling point 80° to 90° C./11 mm Hg were obtained. ##STR14## while cooling The yellowish solution was then stirred at 20° C. for a further 1 hour The ether phase was separated off washed several times with water dried over sodium sulphate After distilling off the solvent the residue was distilled under a water-pump vacuum

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

実験手順: 480 g of bromine were slowly added dropwise to a mixture of 354 g (3 mol) of 3,3-dimethyl-4-fluoro-2-butanone (see Example 1) and 2000 ml of ether at 20° to 30° C., while cooling and stirring. The yellowish solution was then stirred at 20° C. for a further 1 hour, and 500 ml of water were subsequently added carefully. The ether phase was separated off, washed several times with water and dried over sodium sulphate. After distilling off the solvent, the residue was distilled under a water-pump vacuum. 472 g (80% of theory) of 1-bromo-3,3-dimethyl-4-fluoro-2-butanone of boiling point 80° to 90° C./11 mm Hg were obtained. ##STR14## while cooling The yellowish solution was then stirred at 20° C. for a further 1 hour The ether phase was separated off washed several times with water dried over sodium sulphate After distilling off the solvent the residue was distilled under a water-pump vacuum

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

実験手順: 480 g of bromine were slowly added dropwise to a mixture of 354 g (3 mols) of 3,3-dimethyl-4-fluoro-2-butanone and 2,000 ml of ether at 20° to 30° C., while cooling and stirring. The yellowish solution was subsequently stirred at 20° C. for a further hour and 500 ml of water were then carefully added. The ether phase was separated off, washed several times with water and dried over sodium sulphate. After distilling off the solvent, the residue was distilled under a waterpump vacuum. 472 g (80% of theory) of 1-bromo-3,3-dimethyl-4-fluoro-2-butanone of boiling point 80°-90° C./11 mm Hg were obtained. ##STR81## while cooling The yellowish solution was subsequently stirred at 20° C. for a further hour The ether phase was separated off washed several times with water dried over sodium sulphate After distilling off the solvent the residue was distilled under a waterpump vacuum

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

実験手順: 480 g of bromine were slowly added dropwise to a mixture of 354 g (3 mols) of 3,3-dimethyl-4-fluoro-2-butanone and 2,000 ml of ether at 20° to 30° C., while cooling and stirring. The yellowish solution was subsequently stirred for a further hour at 20° C. and 500 ml of water were then carefully added. The ether phase was separated off, washed several times with water and dried over sodium sulphate. After distilling off the solvent, the residue was distilled under a waterpump vacuum. 472 g (80% of theory) of 1-bromo-3,3-dimethyl-4-fluoro-2-butanone of boiling point 80°-90° C./11 mm Hg were obtained. ##STR81## while cooling The yellowish solution was subsequently stirred for a further hour at 20° C. The ether phase was separated off washed several times with water dried over sodium sulphate After distilling off the solvent the residue was distilled under a waterpump vacuum

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

実験手順: 480 g of bromine were slowly added dropwise to a mixture of 354 g (3 mol) of 3,3-dimethyl-4-fluoro-2-butanone and 2,000 ml of ether at 20° C. to 30° C., while cooling and stirring. The yellowish solution was subsequently stirred for a further 1 hour at 20° C. and 500 ml of water were then carefully added. The ether phase was separated off, washed several times with water and dried over sodium sulphate. After distilling off the solvent, the residue was distilled under a waterpump vacuum. 472 g (80% of theory) of 1-bromo-3,3-dimethyl-4-fluoro-2-butanone of boiling point 80°-90° C./11 mm Hg were obtained. ##STR29## while cooling The yellowish solution was subsequently stirred for a further 1 hour at 20° C. The ether phase was separated off washed several times with water dried over sodium sulphate After distilling off the solvent the residue was distilled under a waterpump vacuum