difluoromethane

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

実験手順: A suspension of 341.5 g (l.75 mol) of 2-mercapto-5-pyrid-2-yl-1,3,4-thiadiazole in 4000 ml of dioxane is added to a solution of 230.5 g of 85% potassium hydroxide in 800 ml of water. Then 10 g of potassium iodide and 6 g of tributylammonium bromide are added to the reaction mixture and 750 g (~8.6 mol) of gaseous difluoromethane are introduced over 41/2 hours at 22°-37° C. After evaporating off the dioxane, the reaction mixture is diluted with ethyl acetate, the aqueous phase is separated and the organic solution is washed cold with 1N sodium hydroxide and water, dried over sodium sulfate and clarified with activated carbon. They ethyl acetate is removed under vacuum and the residue is crystallised from ethyl acetate/hexane, affording 321.9 g (75.1%) of the title compound with a melting point of 90°-92° C. are introduced over 41/2 hours at 22°-37° C After evaporating off the dioxane the reaction mixture is diluted with ethyl acetate the aqueous phase is separated the organic solution is washed cold with 1N sodium hydroxide and water dried over sodium sulfate They ethyl acetate is removed under vacuum the residue is crystallised from ethyl acetate/hexane

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

実験手順: Mixtures of CFC-114a, HCFC-22 and hydrogen were fed to a reactor operated at several temperatures for 40 hours. For a 10.5 hour period at 600° C., at an average time in synthesis of 14 hours, with liquid feed rates of 5.5 mL/hr of CFC-114a and 1 mL/hr of HCFC-22, a hydrogen feed rate of 250 cc/min (1 atm. and room temperature basis); a molar ratio of hydrogen to (HFC-114 at HCFC-22) of 10:1 was provided, and the organic component of the reactor effluent contained an average (area percent) of 51.6% HFC-134a, 35.6% HCFC-124, 0.22% CFC-114a, 4.1% HFC-32 and 5.4% HCFC-22.

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

実験手順: Mixtures of CFC-114a, HCFC-22 and hydrogen were fed to a reactor operated at several temperatures for 40 hours. For a 10.5 hour period at 600° C., at an average time in synthesis of 14 hours, with liquid feed rates of 5.5 mL/hr of CFC-114a and 1 mL/hr of HCFC-22, a hydrogen feed rate of 250 cc/min (1 atm. and room temperature basis); a molar ratio of hydrogen to (HFC-114 at HCFC-22) of 10:1 was provided, and the organic component of the reactor effluent contained an average (area percent) of 51.6% HFC-134a, 35.6% HCFC-124, 0.22% CFC-114a, 4.1% HFC-32 and 5.4% HCFC-22.

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

実験手順: A suspension of 341.5 g (l.75 mol) of 2-mercapto-5-pyrid-2-yl-1,3,4-thiadiazole in 4000 ml of dioxane is added to a solution of 230.5 g of 85% potassium hydroxide in 800 ml of water. Then 10 g of potassium iodide and 6 g of tributylammonium bromide are added to the reaction mixture and 750 g (~8.6 mol) of gaseous difluoromethane are introduced over 41/2 hours at 22°-37° C. After evaporating off the dioxane, the reaction mixture is diluted with ethyl acetate, the aqueous phase is separated and the organic solution is washed cold with 1N sodium hydroxide and water, dried over sodium sulfate and clarified with activated carbon. They ethyl acetate is removed under vacuum and the residue is crystallised from ethyl acetate/hexane, affording 321.9 g (75.1%) of the title compound with a melting point of 90°-92° C. are introduced over 41/2 hours at 22°-37° C After evaporating off the dioxane the reaction mixture is diluted with ethyl acetate the aqueous phase is separated the organic solution is washed cold with 1N sodium hydroxide and water dried over sodium sulfate They ethyl acetate is removed under vacuum the residue is crystallised from ethyl acetate/hexane

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

実験手順: A suspension of 341.5 g (l.75 mol) of 2-mercapto-5-pyrid-2-yl-1,3,4-thiadiazole in 4000 ml of dioxane is added to a solution of 230.5 g of 85% potassium hydroxide in 800 ml of water. Then 10 g of potassium iodide and 6 g of tributylammonium bromide are added to the reaction mixture and 750 g (~8.6 mol) of gaseous difluoromethane are introduced over 41/2 hours at 22°-37° C. After evaporating off the dioxane, the reaction mixture is diluted with ethyl acetate, the aqueous phase is separated and the organic solution is washed cold with 1N sodium hydroxide and water, dried over sodium sulfate and clarified with activated carbon. They ethyl acetate is removed under vacuum and the residue is crystallised from ethyl acetate/hexane, affording 321.9 g (75.1%) of the title compound with a melting point of 90°-92° C. are introduced over 41/2 hours at 22°-37° C After evaporating off the dioxane the reaction mixture is diluted with ethyl acetate the aqueous phase is separated the organic solution is washed cold with 1N sodium hydroxide and water dried over sodium sulfate They ethyl acetate is removed under vacuum the residue is crystallised from ethyl acetate/hexane

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

実験手順: Mixtures of CFC-114a, HCFC-22 and hydrogen were fed to a reactor operated at several temperatures for 40 hours. For a 10.5 hour period at 600° C., at an average time in synthesis of 14 hours, with liquid feed rates of 5.5 mL/hr of CFC-114a and 1 mL/hr of HCFC-22, a hydrogen feed rate of 250 cc/min (1 atm. and room temperature basis); a molar ratio of hydrogen to (HFC-114 at HCFC-22) of 10:1 was provided, and the organic component of the reactor effluent contained an average (area percent) of 51.6% HFC-134a, 35.6% HCFC-124, 0.22% CFC-114a, 4.1% HFC-32 and 5.4% HCFC-22.

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

実験手順: Typical compounds conforming to the above general formula are CH3Cl, CH2Cl2, CHCl3, CCl4, CH3F, CH2F2, CHF2Cl, and the like. Addition of such compounds to hexafluoropropene thermally is described in J. Fluorine Chemistry 1982, 21, 253-259. For example, CH2Cl2 addition to CF3CF═CF2 at 280° C. is reported to give 85% yield of CHCl2CF2CHFCF3. at 280° C.

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

実験手順: Typical compounds conforming to the above general formula are CH3Cl, CH2Cl2, CHCl3, CCl4, CH3F, CH2F2, CHF2Cl, and the like. Addition of such compounds to hexafluoropropene thermally is described in J. Fluorine Chemistry 1982, 21, 253-259. For example, CH2Cl2 addition to CF3CF═CF2 at 280° C. is reported to give 85% yield of CHCl2CF2CHFCF3. at 280° C.

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

実験手順: Hydrodechlorination of the chlorine-containing saturated impurities CHClF2, CCl2F2, CHClFCF3, CHF2CClF2, CCl2FCF3, CClF2CClF2, and CClF2CF3 having boiling points of -40.8° C., -29.8° C., -12° C., -10.2° C., 3.0° C., 3.6° C., and -38.7° C., respectively, gives CH2F2, CHClF2, CH2FCF3, CHF2CHF2, CHClFCF3, CHF2CClF2, and CHF2CF3 having boiling points of -51.7° C., -40.8° C., -26.5° C., -19.7° C., -12° C., -10.2° C., and -48.5° C., respectively. Further hydrodefluorination of CH2F2 and CH2FCF3 would give CH3F (HFC-41) and CH3CF3 (HFC-143a) boiling at -78.5° C. and -47.6° C., respectively. points of -40.8° C., -29.8° C., -12° C., -10.2° C., 3.0° C., 3.6° C., and -38.7° C.

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

実験手順: To a solution of 6.2 g of 85% potassium hydroxide in 18 ml of water is added a solution of 6 g (0.03 mol) of 2-mercapto-5-pyrazin-2-yl-1,3,4-thiadiazole in 90 ml of dioxane. Then 0.2 g of potassium iodide and 0.2 g of tetrabutylammonium bromide are added to the reaction mixture and 13 g of gaseous difluoromethane are introduced over 6 hours at 22° to 37° C. After evaporating off the dioxane, the reaction mixture is diluted with ethyl acetate, the aqueous phase is separated and the organic solution is washed cold with 1N sodium hydroxide solution and water, dried over sodium sulfate and clarified with activated carbon. The ethyl acetate is removed under vacuum and the residue is crystallised from ethyl acetate/hexane, affording 312 g (43%) of the title compound with a melting point of 113°-115° C. are introduced over 6 hours at 22° to 37° C After evaporating off the dioxane the reaction mixture is diluted with ethyl acetate the aqueous phase is separated the organic solution is washed cold with 1N sodium hydroxide solution and water dried over sodium sulfate The ethyl acetate is removed under vacuum the residue is crystallised from ethyl acetate/hexane

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

実験手順: A suspension of 16.4 g of 2-amino-4,6-dichloro-pyrimidine in 100 ml of 40% sodium hydroxide solution is stirred for 1 hour at a temperature of 95° to 100° C. After the addition of 200 ml of dioxane, there are added at a temperature of 70° to 75° C., within 1 hour, 20 g of gaseous difluoromethane. The organic phase is separated, and concentrated to about 1/5 of its volume; it is then poured into water and the solid precipitate is removed. The yield is 6 g of 2-amino-4-chloro-6-difluoromethoxy-pyrimidine, m.p. 118° to 119° C. (compound No. 1.7). are added at a temperature of 70° to 75° C., within 1 hour The organic phase is separated concentrated to about 1/5 of its volume it is then poured into water the solid precipitate is removed

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

実験手順: A suspension of 16.4 g of 2-amino-4,6-dichloropyrimidine in 100 ml of 40% sodium hydroxide solution is stirred for 1 hour at a temperature of 95° to 100° C. After the addition of 200 ml of dioxane, there are added at a temperature of 70° to 75° C., within 1 hour, 20 g of gaseous difluoromethane. The organic phase is separated, and concentrated to about 1/5 of its volume; it is then poured into water and the solid precipitate is removed. The yield is 6 g of 2-amino-4-chloro-6-difluoromethoxy-pyrimidine, m.p. 118° to 119° C. (compound No. 1.7). are added at a temperature of 70° to 75° C., within 1 hour The organic phase is separated concentrated to about 1/5 of its volume it is then poured into water the solid precipitate is removed