1,1,1,3,3,3-hexafluoropropan-2-one;trihydrate

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

実験手順: Into a mixture of 2-methyl-7-nitrobenzo[b]furan (200 mg) and aluminum chloride (301 mg) in dichloromethane was passed hexafluoroacetone gas which was made from hexafluoroacetone trihydrate (4.7 ml) and conc. sulfuric acid (15 ml). The mixture was stirred at ambient temperature for 4 hours and then, cooled to 4° C. To the mixture was added 1N-hydrochloric acid dropwise. The organic layer was separated, washed with brine, dried over sodium sulfate and concentrated in vacuo. The residue was purified by column chromatography on silica gel and the obtained oil was crystallized from n-hexane to give 3-(1-hydroxy-2,2,2-trifluoro-1-trifluoromethylethyl)-2-methyl-7-nitrobenzo[b]furan (265 mg). cooled to 4° C The organic layer was separated washed with brine dried over sodium sulfate concentrated in vacuo The residue was purified by column chromatography on silica gel the obtained oil was crystallized from n-hexane

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

実験手順: The title compound was prepared from commercially available of 4-methylthiazol-2-amine (Aldrich) and hexafluoroacetone trihydrate (Aldrich) according to the procedure described in European Journal of Organic Chemistry, (21), 4286-4291; 2003. MS (ESI+) m/z 281 (M+H)+.

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

実験手順: The title compound was prepared from commercially available of 4-methylthiazol-2-amine (Aldrich) and hexafluoroacetone trihydrate (Aldrich) according to the procedure described in European Journal of Organic Chemistry, (21), 4286-4291; 2003. MS (ESI+) m/z 281 (M+H)+.

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

実験手順: In this single stage case, the hexafluoroacetone (6FK) produced may be assayed by continuous adsorption in water. Hexafluoroacetone trihydrate (6FK.3H2,0) which was produced may then be determined by direct GLC analysis using an internal standard. Alternatively, 6FK.3H2, may be determined by potentiometric titration against a standard NaOH. Titer to pH of 4 is due to hydrogenfluoride, if present; titer from pH of 4 to pH of 9 is due to 6FK.3H2 0. Optionally, the 6FK may be recovered by passage through a dry ice condensing system to give 6FK liquid (BP-28° C.).

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

実験手順: In this single stage case, the hexafluoroacetone (6FK) produced may be assayed by continuous adsorption in water. Hexafluoroacetone trihydrate (6FK.3H2,0) which was produced may then be determined by direct GLC analysis using an internal standard. Alternatively, 6FK.3H2, may be determined by potentiometric titration against a standard NaOH. Titer to pH of 4 is due to hydrogenfluoride, if present; titer from pH of 4 to pH of 9 is due to 6FK.3H2 0. Optionally, the 6FK may be recovered by passage through a dry ice condensing system to give 6FK liquid (BP-28° C.).

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

実験手順: The title compound was prepared from commercially available of 4-methylthiazol-2-amine (Aldrich) and hexafluoroacetone trihydrate (Aldrich) using the procedure described in European Journal of Organic Chemistry, (21), 4286-4291; 2003. MS (ESI+) m/z 281 (M+H)+.

反応条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The compound was prepared in analogy to W. Steglich et al., Chem. Ber., 107:1488-1498 (1974). Anhydrous hexafluoroacetone (HFA) was prepared by adding HFA trihydrate dropwise to concentrated sulfuric acid heated to 80° C. The resulting gas was once more washed with concentrated sulfuric acid and then passed into the gas space of the reaction flask. A reflux condenser packed with acetone/dry ice was fitted on the gas outlet of the flask. The compound was prepared in analogy to W The resulting gas was once more washed with concentrated sulfuric acid A reflux condenser packed with acetone/dry ice was fitted on the gas outlet of the flask

反応条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The compound was prepared in analogy to W. Steglich et al., Chem. Ber., 107:1488-1498 (1974). Anhydrous hexafluoroacetone (HFA) was prepared by adding HFA trihydrate dropwise to concentrated sulfuric acid heated to 80° C. The resulting gas was once more washed with concentrated sulfuric acid and then passed into the gas space of the reaction flask. A reflux condenser packed with acetone/dry ice was fitted on the gas outlet of the flask. The compound was prepared in analogy to W The resulting gas was once more washed with concentrated sulfuric acid A reflux condenser packed with acetone/dry ice was fitted on the gas outlet of the flask

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 100 g (0.38 mol) of 1-fluoro-4,4-bis(trifluoromethyl)-2,3,5-trioxolanyl methyl ether (purity: 98%) was charged in a 500-ml five-necked flask. While performing nitrogen bubbling, brine at −20° C. was passed through a Dimroth condenser. While stirring at a reaction temperature of −20° C., 23.4 g (0.38 mol) of dimethyl sulfide was added dropwise using a dropping funnel over 30 minutes. The gas obtained by the reaction was collected by a water trap cooled with ice water to 0° C., and the obtained aqueous layer was analyzed by 19F-NMR. As a result, it was confirmed that 73.8 g (yield: 89%) of hexafluoroacetone trihydrate was obtained. at −20° C. was added dropwise over 30 minutes The gas obtained by the reaction was collected by a water trap

反応条件: temp:130.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Hexafluoroacetone trihydrate (9.68 g, 44 mmol) was added to 2,6-dimethylaniline (4.84 g, 40 mmol) and p-toluenesulfonic acid (304 mg, 1.6 mmol) at room temperature. The mixture was stirred at 130° C. for 14 hours under a nitrogen atmosphere. After cooling down, the solidified mixture was washed with sodium bicarbonate solution, water, and hexane and dried to afford 10 g of 4-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]-2,6-dimethylaniline. 1H NMR (DMSO): δ 8.11 (s, 1H), 7.08 (s, 2H), 4.89 (s, 2H), 2.10 (s, 6H). MS (ES) m/z 288.1 ([M+H]+). After cooling down the solidified mixture was washed with sodium bicarbonate solution, water, and hexane dried

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

実験手順: Into a mixture of 2-methyl-7-nitrobenzo[b]furan (200 mg) and aluminum chloride (301 mg) in dichloromethane was passed hexafluoroacetone gas which was made from hexafluoroacetone trihydrate (4.7 ml) and conc. sulfuric acid (15 ml). The mixture was stirred at ambient temperature for 4 hours and then, cooled to 4° C. To the mixture was added 1N-hydrochloric acid dropwise. The organic layer was separated, washed with brine, dried over sodium sulfate and concentrated in vacuo. The residue was purified by column chromatography on silica gel and the obtained oil was crystallized from n-hexane to give 3-(1-hydroxy-2,2,2-trifluoro-1-trifluoromethylethyl)-2-methyl-7-nitrobenzo[b]furan (265 mg). cooled to 4° C The organic layer was separated washed with brine dried over sodium sulfate concentrated in vacuo The residue was purified by column chromatography on silica gel the obtained oil was crystallized from n-hexane

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

実験手順: The title compound was prepared from commercially available of 4-methylthiazol-2-amine (Aldrich) and hexafluoroacetone trihydrate (Aldrich) according to the procedure described in European Journal of Organic Chemistry, (21), 4286-4291; 2003. MS (ESI+) m/z 281 (M+H)+.