1,1,1-trifluoropentane-2,4-dione

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

実験手順: A mixture of 1,1,1-trifluoro-2,4-pentanedione (0.02 mol, 2.4 mL) and 4-methoxyphenyl hydrazine.HCl (4.54 g, 1.3 eq.) in 2-methoxyethanol (100 mL) and acetic acid (30 mL) was refluxed for 6 h. The reaction mixture was evaporated and purified by flash chromatography on a silica gel column (400 g) eluted with 4:1 hexane:ethyl acetate to give 4.5 g of pure product (88%). was refluxed for 6 h The reaction mixture was evaporated purified by flash chromatography on a silica gel column (400 g) eluted with 4:1 hexane

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

実験手順: 300 mg of 2-methoxyphenyl hydrazine hydrochloride was dissolved in 1.3 ml of 2-methoxyethanol, and 2.5 ml of acetic acid and 208 μl of 1,1,1-trifluoro-2,4-pentanedione were added and heated at reflux for 1 hour and 40 minutes. The solvent was distilled off under reduced pressure, and 50 ml of ethyl acetate was added, and the organic layer was washed with 50 ml of a saturated sodium bicarbonate solution and 50 ml of saturated saline and dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to yield 485.6 mg of the title compound. heated at reflux for 1 hour and 40 minutes The solvent was distilled off under reduced pressure, and 50 ml of ethyl acetate was added the organic layer was washed with 50 ml of a saturated sodium bicarbonate solution and 50 ml of saturated saline dried over anhydrous magnesium sulfate the solvent was distilled off under reduced pressure

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

実験手順: To a solution 25.0 grams of 1,1,1,-trifluoro-2,4-pentanedione in 150 ml of ethanol (anhydrous, 5% methanol) at 10 C. was added dropwise over 35 minutes a solution 8.3 grams of methyl hydrazine in 25 ml of ethanol. The reaction temperature did not exceed 20 C. After an additional 30 minutes of stirring, the cooling bath was removed and the reaction was allowed to stir for one hour. Then five ml of glacial acetic acid was added and the reaction was refluxed for four hours. The reaction was then concentrated under reduced pressure and 100 ml of toluene was added to help azeotrope the residual acetic acid during a second concentration under reduced pressure. High vacuum was pulled on the sample for one hour at 50 C. to yield 25.3 g of the desired product as an oil. the cooling bath was removed to stir for one hour Then five ml of glacial acetic acid was added the reaction was refluxed for four hours The reaction was then concentrated under reduced pressure and 100 ml of toluene was added during a second concentration under reduced pressure High vacuum was pulled on the sample for one hour at 50 C

反応条件: temp:102.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 28.4 g (0.23 mol) of 2-methoxyaniline and 43.2 g (0.28 mol) of 1,1,1-trifluoro-2,4-pentanedione is prepared and heated at 100-105° C. for 1 h, with stirring. After cooling, the reaction mixture is redissolved in ethyl ether and the solution obtained is dried over sodium sulfate and then concentrated under reduced pressure to give 59.1 g of the expected product in the form of a beige solid (yield=99%). is prepared After cooling the solution obtained is dried over sodium sulfate concentrated under reduced pressure

反応条件: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A suspension of 24 g (0.1 mole) of 2-trifluoromethylphenyl-guanidinium hydrochloride in 80 ml of tetrahydrofuran is added to a solution of 12 g (0.1 mole) of potassium tert.-butoxide in 100 ml of tetrahydrofuran. When the exothermic reaction has subsided, 15.4 g (0.1 mole) of α,α,α-trifluoroacetylacetone in 20 ml of tetrahydrofuran are added. The reaction mixture is stirred for 2 hours at 60° C., then concentrated by evaporation in a rotary evaporator. The residue is chromatographed on silica gel with a mixture of ethyl acetate and hexane (ratio 1:2). 18.7 g (58 2% of the theoretical amount) of the title compound of formula ##STR16## are obtained in the form of crystals having a melting point of 65°-66° C. (Comp. No. 2.020). When the exothermic reaction concentrated by evaporation in a rotary evaporator The residue is chromatographed on silica gel with a mixture of ethyl acetate and hexane (ratio 1:2)

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

実験手順: To a suspension of 4-fluoro-3-cyanophenylhydrazine tin chloride (20 g, 53.6 mmol) in ethanol (150 mL) was added 1,1,1-trifluoro-2,4-pentanedione (8.18 g, 53.6 mmol). The reaction was brought to reflux overnight. The next day the ethanol was evaporated and the residue partitioned between ethyl acetate and HCl (1 N). The aqueous phase was extracted with ethyl acetate (4×20 mL). The organic phase is washed with water, brine, dried over sodium sulfate, filtered and concentrated. Flash chromatography gave 1-(4-fluoro-3-cyanophenyl)-3-trifluoromethyl-5-methylpyrazole (8 g, 56% yield) as pure compound: MS (CI): 270 (M+H)+ (100%). to reflux overnight The next day the ethanol was evaporated the residue partitioned between ethyl acetate and HCl (1 N) The aqueous phase was extracted with ethyl acetate (4×20 mL) The organic phase is washed with water, brine dried over sodium sulfate filtered concentrated

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

実験手順: To a suspension of 4-fluoro-3-cyanophenylhydrazine tin chloride (20 g, 53.6 mmol) in ethanol (150 mL) was added 1,1,1-trifluoro-2,4-pentanedione (8.18 g, 53.6 mmol). The reaction was brought to reflux overnight. The next day the ethanol was evaporated and the residue partitioned between ethyl acetate and HCl (1 N). The aqueous phase was extracted with ethyl acetate (4×20 mL). The organic phase is washed with water, brine, dried over sodium sulfate, filtered and concentrated. Flash chromatography gave 1-(4-fluoro-3-cyanophenyl)-3-trifluoromethyl-5-methylpyrazole (8 g, 56% yield) as pure compound: MS (CI): 270 (M+H)+ (100%). to reflux overnight The next day the ethanol was evaporated the residue partitioned between ethyl acetate and HCl (1 N) The aqueous phase was extracted with ethyl acetate (4×20 mL) The organic phase is washed with water, brine dried over sodium sulfate filtered concentrated

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

実験手順: This material was prepared in 84% yield from 3-amino-5-benzylthio-1,2,4-triazole and 1,1,1-trifluoro2,4-pentanedione following the general procedure described in EXAMPLE 34. The product was purified by recrystallization from benzene-hexane to yield a tan solid, m.p. 83.5°-84.5° C. IR, 1H NMR and 19F NMR spectra were in agreement with the assigned structure. The product was purified by recrystallization from benzene-hexane to yield a tan solid, m.p. 83.5°-84.5° C

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

実験手順: Into 100 ml of an ethanolic solution of 25 g (0.16 mol) of trifluoroacetylacetone, there was added dropwise 7.4 g (0.16 mol) of methylhydrazine. After stirring at room temperature for 3 hours, the mixture was left to stand overnight and the solvent was evaporated to give 19.2 g of 1,5-dimethyl-3-trifluoromethylpyrazole as an oil. Following then the procedures as Reference example 1, this product was allowed to react with chlorosulfonic acid and then with thionyl chloride to obtain 29 g of 1,5-dimethyl-3-trifluoromethylpyrazole-4-sulfonyl-chloride, which was in turn reacted with aqueous ammonia (28%) in tetrahydrofuran to give 21.5 g of 1,5-dimethyl-3-trifluoromethylpyrazole-4-sulfonamide melting at 204°-206° C. the mixture was left to stand overnight the solvent was evaporated

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

実験手順: A mixture of 2.19 g (8.00 mmol) of N-(5-amino-1,2,4-triazol-3-yl)-2-chlorobenzenesulfonamide and 1.09 ml (1.38 g, 8.96 mmol) of 1,1,1-trifluoro-2,4-pentane-dione in 9 ml of glacial acetic acid was heated at reflux for 21 hours. After cooling to room temperature, the reaction mixture was poured into a mixture of ice and water. The solid which separated was collected by filtration, washed with water and dried to yield 2.90 g (93 percent) of the desired product as a white solid, mp 203°-204.5° C. IR and 1H NMR spectra were in agreement with the assigned structure. was heated at reflux for 21 hours The solid which separated was collected by filtration washed with water dried

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

実験手順: Hydroxy(tosyloxy)iodobenzene (78.5 g) was added to a solution of 1,1,1-trifluoropentane-2,4-dione in acetonitrile (500 ml). The mixture was heated under reflux for 45 minutes, then cooled, and thiourea (15.2 g) was added. The mixture was heated under reflux for 4 hours and then left to stand overnight. Evaporation and crystallisation of the residue from dichloromethane gave the title compound. The mixture was heated under reflux for 45 minutes cooled The mixture was heated under reflux for 4 hours left Evaporation and crystallisation of the residue from dichloromethane

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

実験手順: Hydroxy(tosyloxy)iodobenzene (78.5 g) was added to a solution of 1,1,1-trifluoropentane-2,4-dione in acetonitrile (500 ml). The mixture was heated under reflux for 45 minutes, then cooled, and thiourea (15.2 g) was added. The mixture was heated under reflux for 4 hours and then left to stand overnight. Evaporation and crystallisation of the residue from dichloromethane gave the title compound. The mixture was heated under reflux for 45 minutes cooled The mixture was heated under reflux for 4 hours left Evaporation and crystallisation of the residue from dichloromethane