1,1,1,3,4,4,5,5,5-nonafluoro-2-(trifluoromethyl)pent-2-ene

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:-0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: In a 21 3-kneck flask equipped with condenser, thermometer, and a dropping funnel 1300 ml methylene chloride and perfluoro-2-methyl-2-pentene (197 g, 0.65 mol) was placed, and then 117 ml water were added. The mixture was cooled to −0° C. and Et3N (164 g, 1.62 mol) was added at a temperature ranging from −5° to 5° C. The mixture was stirred at this temperature for 15 min and a solution of 75 ml N-methylhydrazine in water (40% w.w.) was slowly added to this mixture at 5° C. within 2 h. The reaction mixture was stirred for 15-20 h at 20° C. The mixture was washed with water, the organic layer was dried over Na2SO4 and the solvent was distilled off under atmospheric pressure. The crude product was purified via vacuum distillation. The yield of N-Methyl-3-pentafluoroethyl-4-trifluoromethyl-5-fluoro-1H-pyrazole was 158 g (85% yield). Boiling point 62-67° C. at 15-20 mbar. In a 21 3-kneck flask equipped with condenser ranging from −5° to 5° C The reaction mixture was stirred for 15-20 h at 20° C The mixture was washed with water the organic layer was dried over Na2SO4 the solvent was distilled off under atmospheric pressure The crude product was purified via vacuum distillation

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

実験手順: In a 3-kneck flask equipped with condenser, thermometer, and a dropping funnel 130 ml methylene chloride and perfluoro-2-methyl-2-pentene (19.6 g, 0.065 mol) was placed and then 15 ml water were added. The mixture was cooled to 0° C. and Et3N (16.4 g, 0.16 mol) was added at a temperature ranging from 0° C. to 5° C. The mixture was stirred at this temperature for 15 min and 40% solution of methylhydrazine in water (7.4 g) was slowly added to this mixture at 0° C. The reaction mixture was stirred for 1 h at 5° C. and finally for 1.5 h at 20° C. The mixture was washed with water (3×50 ml), the organic layer was dried over Na2SO4 and the solvent was distilled off under atmospheric pressure. The crude product was purified via vacuum distillation. The yield of N-methyl-3-pentafluoroethyl-4-trifluoromethyl-5-fluoro-1H-pyrazole was 13.9 g. (75%), boiling point 62-65° C. at 17 mbar. In a 3-kneck flask equipped with condenser ranging from 0° C. to 5° C The reaction mixture was stirred for 1 h at 5° C. and finally for 1.5 h at 20° C The mixture was washed with water (3×50 ml) the organic layer was dried over Na2SO4 the solvent was distilled off under atmospheric pressure The crude product was purified via vacuum distillation

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

実験手順: In a 3-kneck flask equipped with condenser, thermometer, and a dropping funnel 130 ml methylene chloride and perfluoro-2-methyl-2-pentene (19.6 g, 0.065 mol) was placed and then 15 ml water were added. The mixture was cooled to 0° C. and Et3N (16.4 g, 0.16 mol) was added at a temperature ranging from 0° C. to 5° C. The mixture was stirred at this temperature for 15 min and 40% solution of methylhydrazine in water (7.4 g) was slowly added to this mixture at 0° C. The reaction mixture was stirred for 1 h at 5° C. and finally for 1.5 h at 20° C. The mixture was washed with water (3×50 ml), the organic layer was dried over Na2SO4 and the solvent was distilled off under atmospheric pressure. The crude product was purified via vacuum distillation. The yield of N-methyl-3-pentafluoroethyl-4-trifluoromethyl-5-fluoro-1H-pyrazole was 13.9 g. (75%), boiling point 62-65° C. at 17 mbar. In a 3-kneck flask equipped with condenser ranging from 0° C. to 5° C The reaction mixture was stirred for 1 h at 5° C. and finally for 1.5 h at 20° C The mixture was washed with water (3×50 ml) the organic layer was dried over Na2SO4 the solvent was distilled off under atmospheric pressure The crude product was purified via vacuum distillation

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

実験手順: Methyl fluorosulfate (7.6 g, 0.0665 mol) was added dropwise at 0° to a stirred solution of tris(dimethylamino)sulfonium 1,1,1,3,3,4,4,5,5,5-decafluoro-2-(trifluoromethyl)-2-pentanide, prepared by dissolving 20.2 g (0.073 mol) of tris(dimethylamino)sulfonium difluorotrimethylsilicate and 20.0 g (0.0665 mol) of 1,1,1,3,4,4,5,5,5-nonafluoro-2-trifluoromethyl-2-pentene in 75 mL of benzonitrile. The reaction mixture was warmed at 25°, and the most volatile portion of the reaction mixture was distilled out under reduced pressure. The distillate was redistilled at atmospheric pressure to give 13.27 g (60%) of 3,3,4,4,5,5,5-heptafluoro-2,2-bis(trifluoromethyl)pentane as a colorless liquid: b.p. 88°-89°; 19F NMR (CCl3F) δ -67.7 ppm (t,t 6F), -81.1 ppm (t, 3F), -110.5 ppm (m, 2F) and -123.7 ppm (m, 2F); 1H NMR (CCl3F) δ 1.72 ppm. Anal. Calcd. for C7H3F13 : C, 25.17; H, 0.91; F, 73.93. Found: C, 24.88; H, 0.87; F, 73.64. prepared The reaction mixture was warmed at 25° the most volatile portion of the reaction mixture was distilled out under reduced pressure The distillate was redistilled at atmospheric pressure

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

実験手順: Methyl fluorosulfate (7.6 g, 0.0665 mol) was added dropwise at 0° to a stirred solution of tris(dimethylamino)sulfonium 1,1,1,3,3,4,4,5,5,5-decafluoro-2-(trifluoromethyl)-2-pentanide, prepared by dissolving 20.2 g (0.073 mol) of tris(dimethylamino)sulfonium difluorotrimethylsilicate and 20.0 g (0.0665 mol) of 1,1,1,3,4,4,5,5,5-nonafluoro-2-trifluoromethyl-2-pentene in 75 mL of benzonitrile. The reaction mixture was warmed at 25°, and the most volatile portion of the reaction mixture was distilled out under reduced pressure. The distillate was redistilled at atmospheric pressure to give 13.27 g (60%) of 3,3,4,4,5,5,5-heptafluoro-2,2-bis(trifluoromethyl)pentane as a colorless liquid: b.p. 88°-89°; 19F NMR (CCl3F) δ -67.7 ppm (t,t 6F), -81.1 ppm (t, 3F), -110.5 ppm (m, 2F) and -123.7 ppm (m, 2F); 1H NMR (CCl3F) δ 1.72 ppm. Anal. Calcd. for C7H3F13 : C, 25.17; H, 0.91; F, 73.93. Found: C, 24.88; H, 0.87; F, 73.64. prepared The reaction mixture was warmed at 25° the most volatile portion of the reaction mixture was distilled out under reduced pressure The distillate was redistilled at atmospheric pressure

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

実験手順: 1.0 g (7.0 mmol) of 3-chloro-2-hydrazinopyridine is suspended in 2.9 ml (21 mmol) of triethylamine and 40.0 ml of acetonitrile and, at −65° C., added to 2.1 g (7 mmol) of (1,1,1,3,4,4,5,5,5-nonafluoro-2-(trifluoromethyl)pent-2-ene. The reaction mixture is slowly heated to room temperature and then stirred at room temperature for 60 hours. The solid is filtered off and afterwashed with diethyl ether. The solvent is removed under reduced pressure on a rotary evaporator. The product is extracted from the residue three times with cyclohexane. The organic phases are combined and the solvent is removed under reduced pressure on a rotary evaporator. This gives 1.95 g of 3-chloro-2-[5-fluoro-3-(pentafluoroethyl)-4-(trifluoromethyl)-1H-pyrazol-1-yl]pyridine (73%) as an orange oil. The solid is filtered off The solvent is removed under reduced pressure on a rotary evaporator The product is extracted from the residue three times with cyclohexane the solvent is removed under reduced pressure on a rotary evaporator

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

実験手順: Methyl fluorosulfate (7.6 g, 0.0665 mol) was added dropwise at 0° to a stirred solution of tris(dimethylamino)sulfonium 1,1,1,3,3,4,4,5,5,5-decafluoro-2-(trifluoromethyl)-2-pentanide, prepared by dissolving 20.2 g (0.073 mol) of tris(dimethylamino)sulfonium difluorotrimethylsilicate and 20.0 g (0.0665 mol) of 1,1,1,3,4,4,5,5,5-nonafluoro-2-trifluoromethyl-2-pentene in 75 mL of benzonitrile. The reaction mixture was warmed at 25°, and the most volatile portion of the reaction mixture was distilled out under reduced pressure. The distillate was redistilled at atmospheric pressure to give 13.27 g (60%) of 3,3,4,4,5,5,5-heptafluoro-2,2-bis(trifluoromethyl)pentane as a colorless liquid: b.p. 88°-89°; 19F NMR (CCl3F) δ -67.7 ppm (t,t, 6F), -81.1 ppm (t, 3F), -110.5 ppm (m, 2F) and -123.7 ppm (m, 2F); 1H NMR (CCl3F) δ1.72 ppm. Anal. Calcd. for C7H3F13 : C, 25.17; H, 0.91; F, 73.93. Found: C, 24.88; H, 0.87; F, 73.64. prepared The reaction mixture was warmed at 25° the most volatile portion of the reaction mixture was distilled out under reduced pressure The distillate was redistilled at atmospheric pressure

反応条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Perfluoro-2-methylpent-2-ene (3 g) and iodine (1.25 g) were sealed in a 10 mL pressure tube. The tube was cooled to -78° C., evacuated, and charged with 1500 psi of hydrogen at room temperature. The tube was then heated at 240° C. for 1 h, and 260° C. for 15 h. The tube was cooled, vented, and opened The liquid was washed with water, giving 1,1,1,2,2,3,5,5,5-nonafluoro-4-trifluoromethylpentane (1.38 g) which was 99.5% pure by GC analysis GC/IR 3000 cm-1, w (C-H); 1288 cm-1 , vs (C-F); 1228 cm-1, vs (C-F); 691 cm-1, m. 19FNMR (CCl3F as internal standard): -62 ppm, c, 3F; -67 5 ppm, c, 3F; -83.9 ppm, t, 3F; -122-133 ppm, AB, 2F; -212.2 ppm, c, 1F. 1HNMR (CHCl3 as internal standard): 5.27 ppm, dd, 1H; 3.55 ppm, c, 1H. The boiling point of this product was 67° C. evacuated charged with 1500 psi of hydrogen at room temperature The tube was then heated at 240° C. for 1 h The tube was cooled was washed with water