3,3,3-trifluoro-2,2-dimethylpropanamide

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

実験手順: A solution of 3,3,3-trifluoro-2,2-dimethylpropionic acid (0.5 g, 3.20 mmol) in DCM (5 mL) was treated with oxalyl chloride (0.350 mL, 4.00 mmol) and 1 drop of DMF, stirred at RT for 1 h, added drop-wise to a solution of NH4OH (˜15M, 5 mL, ˜75 mmol) in THF (5 mL) and stirred at RT overnight. Solids were removed via filtration through diatomaceous earth, rinsed well with 4:1 DCM/THF, the filtrate saturated with solid NaCl, extracted with 4:1 DCM/THF (3×) and the combined organics were dried over Na2SO4 and concentrated to dryness to afford 3,3,3-trifluoro-2,2-dimethylpropanamide (370 mg, 74%). 1H NMR (400 MHz, DMSO-d6): δ 7.42 (s, 1H), 7.35 (s, 1H), 1.29 (s, 6H). stirred at RT overnight Solids were removed via filtration through diatomaceous earth rinsed well with 4:1 DCM/THF the filtrate saturated with solid NaCl, extracted with 4:1 DCM/THF (3×) the combined organics were dried over Na2SO4 concentrated to dryness

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

実験手順: A mixture of 1.05 g (6.77 mmol) 3,3,3-trifluoro-2,2-dimethyl-propionamide and 1.48 g (3.66 mmol) Lawesson's reagent in 32 ml dry THF was stirred at reflux temperature for 20 h. After that the reaction mixture was cooled to room temperature and concentrated in vacuo. The residue was purified by chromatography on silicagel (heptane, EtOAc) to afford 0.81 g of the title compound as pure white crystals. MS: M+H=172. at reflux temperature for 20 h concentrated in vacuo The residue was purified by chromatography on silicagel (heptane, EtOAc)

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

実験手順: A mixture of 2 g (12.81 mmol) 3,3,3-trifluoro-2,2-dimethylpropionic acid (Aldrich), 2.077 g (12.81 mmol) carbonyl-diimidazole and 5.55 ml (64.1 mmol) aqueous ammonia in 50 ml CH2Cl2 was stirred at room temperature for 20 h. After that, diethyl ether was added and the resulting mixture was washed with 0.1 N HCL, 0.1 N NaOH, water and brine. The organic layer was dried (MgSO4), filtered and concentrated in vacuo to afford 1.15 g of the title compound as white crystals, that were used in the next step without further purification. MS: M+H=156. the resulting mixture was washed with 0.1 N HCL, 0.1 N NaOH, water and brine The organic layer was dried (MgSO4) filtered concentrated in vacuo

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

実験手順: Oxalyl chloride (140.8 mmol) was added dropwise to a solution of 3,3,3-trifluoro-2,2-dimethyl-propionic acid [889940-13-0] (128 mmol) in CH2Cl2 (128 mL) at 0° C. Added a few dr DMF until gas evolution was observed and then continued stirring for 30 min. After warming to rt and stirring overnight, the reaction mixture was concentrated (40° C., 00 mbar). The residue was dissolved in THF (128 mL), cooled to 0° C. and then slowly treated with a solution of concentrated aqueous ammonia (64 mL). After stirring at 0° C. for 30 min and then at rt for 4 h, the reaction mixture was concentrated to half its volume to give a thick white suspension. After filtering and drying, the title compound was obtained as a white solid. ESI-MS: [M+H]+ 156. stirring overnight the reaction mixture was concentrated (40° C., 00 mbar) The residue was dissolved in THF (128 mL) cooled to 0° C. slowly treated with a solution of concentrated aqueous ammonia (64 mL) After stirring at 0° C. for 30 min at rt for 4 h the reaction mixture was concentrated to half its volume to give a thick white suspension After filtering drying

反応条件: temp:200.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 3,3,3-trifluoro-2,2-dimethyl-propionamide (Stage 44.4) (121.2 mmol) and phosphorus pentoxide (121.2 mmol) was slowly heated to 200° C. and the resulting distillate collected. The title compound was obtained as a colorless liquid.

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

実験手順: A solution of 3,3,3-trifluoro-2,2-dimethylpropionic acid (0.5 g, 3.20 mmol) in DCM (5 mL) was treated with oxalyl chloride (0.350 mL, 4.00 mmol) and 1 drop of DMF, stirred at RT for 1 h, added drop-wise to a solution of NH4OH (˜15M, 5 mL, ˜75 mmol) in THF (5 mL) and stirred at RT overnight. Solids were removed via filtration through diatomaceous earth, rinsed well with 4:1 DCM/THF, the filtrate saturated with solid NaCl, extracted with 4:1 DCM/THF (3×) and the combined organics were dried over Na2SO4 and concentrated to dryness to afford 3,3,3-trifluoro-2,2-dimethylpropanamide (370 mg, 74%). 1H NMR (400 MHz, DMSO-d6): δ 7.42 (s, 1H), 7.35 (s, 1H), 1.29 (s, 6H). stirred at RT overnight Solids were removed via filtration through diatomaceous earth rinsed well with 4:1 DCM/THF the filtrate saturated with solid NaCl, extracted with 4:1 DCM/THF (3×) the combined organics were dried over Na2SO4 concentrated to dryness