1,3,3,3-tetrafluoro-1-methoxy-2-(trifluoromethyl)prop-1-ene

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

実験手順: Using essentially the same procedure as in Example 1, an isomeric mixture of the perfluorobutyric acid fluorides (2.67 g with summary acyl fluorides content 81%, 10 mmol), potassium fluoride (0.78 g, 13 mmol), the 1-methoxyheptafluoro-1-isobutene (5.10 g, 96% purity, 23 mmol) was combined in 8.54 g diglyme and agitated at room temperature for 34 hours. The reactor was vented and 5.44 g of material collected in the trap. The material consisted of (GC %): 4.0% starting C4 acyl fluoride, 35.3% C4F9OCH3, 58.5% hexafluoropivaloyl fluoride (C5 acid fluoride) and a trace (0.4%) of diglyme. To the diglyme residue was added 8.64 g H2O and 1.76 g triethylamine to yield 1.38 g CF3CH2CF3 (after recondensation), and 95.5 % purity. The products yields were calculated based on the weight of obtained mixtures, their GC % content and purity of starting compounds. Yield of C4F9OCH3 is 77% (from perfluorobutyric acid fluorides and 85% on the consumed fluorides). Yield of CF3CH2CF3 is 39% and C5 acid fluoride -65%. 5.44 g of material collected in the trap To the diglyme residue was added 8.64 g H2O and 1.76 g triethylamine

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

実験手順: To a rapidly stirred mixture of 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-4-oxapent-2-ene (N-1) (10.0 g, 47.15 mmol) and formamidine acetate (7.37 g, 70.73 mmol) in a mixture of water (50 mL) and dichloromethane (50 mL) at 0° C., a solution of sodium hydroxide (7.54 g, 189 mmol) in water (40 mL) is added dropwise and the resulting mixture is stirred for 30 min after complete addition. The dichloromethane layer is separated, washed with 1M aqueous HCl solution and water, dried over Na2SO4 and filtered. The filtrate is concentrated in vacuo to afford 4-fluoro-6-methoxy-5-(trifluoromethyl)pyrimidine (N-2) as a yellow solid. The product is used directly in the next step without further purification. after complete addition The dichloromethane layer is separated washed with 1M aqueous HCl solution and water dried over Na2SO4 filtered The filtrate is concentrated in vacuo

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

実験手順: Using essentially the same procedure as in Example 1, an isomeric mixture of the perfluorobutyric acid fluorides (2.67 g with summary acyl fluorides content 81%, 10 mmol), potassium fluoride (0.78 g, 13 mmol), the 1-methoxyheptafluoro-1-isobutene (5.10 g, 96% purity, 23 mmol) was combined in 8.54 g diglyme and agitated at room temperature for 34 hours. The reactor was vented and 5.44 g of material collected in the trap. The material consisted of (GC %): 4.0% starting C4 acyl fluoride, 35.3% C4F9OCH3, 58.5% hexafluoropivaloyl fluoride (C5 acid fluoride) and a trace (0.4%) of diglyme. To the diglyme residue was added 8.64 g H2O and 1.76 g triethylamine to yield 1.38 g CF3CH2CF3 (after recondensation), and 95.5 % purity. The products yields were calculated based on the weight of obtained mixtures, their GC % content and purity of starting compounds. Yield of C4F9OCH3 is 77% (from perfluorobutyric acid fluorides and 85% on the consumed fluorides). Yield of CF3CH2CF3 is 39% and C5 acid fluoride -65%. 5.44 g of material collected in the trap To the diglyme residue was added 8.64 g H2O and 1.76 g triethylamine

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

実験手順: 200 g (0.88 moles) of heptafluoroisobutenyl methyl ether (purity: 93%) was charged into a three-necked flask having a capacity of 300 ml, provided with a Dimroth condenser, a stirrer and a gas feed tube, and a brine at -20° C. was passed through the Dimroth condenser. About 340 liters of ozone-containing oxygen gas (ozone concentration: 125 mg/liter) was bubbled through the ether compound at 0° C. with stirring over 11 hours 18 minutes (total ozone amount: about 0.88 moles). After the reaction, 134.8 g of the reaction product was recovered therefrom and distilled, whereby 73.0 g of perfluoro(2-methyl-1,2-epoxypropyl) methyl ether was obtained as a fraction having a boiling point of 82° to 85° C. (yield: 36.5%). provided with a Dimroth condenser, a stirrer and a gas feed tube at -20° C. was bubbled through the ether compound at 0° C. After the reaction, 134.8 g of the reaction product was recovered distilled

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

実験手順: 200 g (0.88 moles) of heptafluoroisobutenyl methyl ether (purity: 93%) was charged into a three-necked flask having a capacity of 300 ml, provided with a Dimroth condenser, a stirrer and a gas feed tube, and a brine at -20° C. was passed through the Dimroth condenser. About 340 liters of ozone-containing oxygen gas (ozone concentration: 125 mg/liter) was bubbled through the ether compound at 0° C. with stirring over 11 hours 18 minutes (total ozone amount: about 0.88 moles). After the reaction, 134.8 g of the reaction product was recovered therefrom and distilled, whereby 73.0 g of perfluoro(2-methyl-1,2-epoxypropyl) methyl ether was obtained as a fraction having a boiling point of 82° to 85° C. (yield: 36.5%). provided with a Dimroth condenser, a stirrer and a gas feed tube at -20° C. was bubbled through the ether compound at 0° C. After the reaction, 134.8 g of the reaction product was recovered distilled

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

実験手順: To a rapidly stirred mixture of 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-4-oxapent-2-ene (N-1) (10.0 g, 47.15 mmol) and formamidine acetate (7.37 g, 70.73 mmol) in a mixture of water (50 mL) and dichloromethane (50 mL) at 0° C., a solution of sodium hydroxide (7.54 g, 189 mmol) in water (40 mL) is added dropwise and the resulting mixture is stirred for 30 min after complete addition. The dichloromethane layer is separated, washed with 1M aqueous HCl solution and water, dried over Na2SO4 and filtered. The filtrate is concentrated in vacuo to afford 4-fluoro-6-methoxy-5-(trifluoromethyl)pyrimidine (N-2) as a yellow solid. The product is used directly in the next step without further purification. after complete addition The dichloromethane layer is separated washed with 1M aqueous HCl solution and water dried over Na2SO4 filtered The filtrate is concentrated in vacuo

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

実験手順: 200 g (0.88 moles) of heptafluoroisobutenyl methyl ether (purity: 93%) was charged into a three-necked flask having a capacity of 300 ml, provided with a Dimroth condenser, a stirrer and a gas feed tube, and a brine at -20° C. was passed through the Dimroth condenser. About 340 liters of ozone-containing oxygen gas (ozone concentration: 125 mg/liter) was bubbled through the ether Compound at 0° C. with stirring over 11 hours 18 minutes (total ozone amount: about 0.88 moles). After the reaction, 134.8 g of the reaction product was recovered therefrom and distilled, whereby 73.0 g of perfluoro(2-methyl-1,2-epoxypropyl) methyl ether was obtained as a fraction having a boiling point of 82° to 85° C. (yield: 36.5%). provided with a Dimroth condenser, a stirrer and a gas feed tube at -20° C. was bubbled through the ether Compound at 0° C. After the reaction, 134.8 g of the reaction product was recovered distilled

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

実験手順: To a rapidly stirred mixture of 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-4-oxapent-2-ene (N-1) (10.0 g, 47.15 mmol) and formamidine acetate (7.37 g, 70.73 mmol) in a mixture of water (50 mL) and dichloromethane (50 mL) at 0° C., a solution of sodium hydroxide (7.54 g, 189 mmol) in water (40 mL) is added dropwise and the resulting mixture is stirred for 30 min after complete addition. The dichloromethane layer is separated, washed with 1M aqueous HCl solution and water, dried over Na2SO4 and filtered. The filtrate is concentrated in vacuo to afford 4-fluoro-6-methoxy-5-(trifluoromethyl)pyrimidine (N-2) as a yellow solid. The product is used directly in the next step without further purification. after complete addition The dichloromethane layer is separated washed with 1M aqueous HCl solution and water dried over Na2SO4 filtered The filtrate is concentrated in vacuo

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

実験手順: Using essentially the same procedure as in Example 1, an isomeric mixture of the perfluorobutyric acid fluorides (2.67 g with summary acyl fluorides content 81%, 10 mmol), potassium fluoride (0.78 g, 13 mmol), the 1-methoxyheptafluoro-1-isobutene (5.10 g, 96% purity, 23 mmol) was combined in 8.54 g diglyme and agitated at room temperature for 34 hours. The reactor was vented and 5.44 g of material collected in the trap. The material consisted of (GC %): 4.0% starting C4 acyl fluoride, 35.3% C4F9OCH3, 58.5% hexafluoropivaloyl fluoride (C5 acid fluoride) and a trace (0.4%) of diglyme. To the diglyme residue was added 8.64 g H2O and 1.76 g triethylamine to yield 1.38 g CF3CH2CF3 (after recondensation), and 95.5 % purity. The products yields were calculated based on the weight of obtained mixtures, their GC % content and purity of starting compounds. Yield of C4F9OCH3 is 77% (from perfluorobutyric acid fluorides and 85% on the consumed fluorides). Yield of CF3CH2CF3 is 39% and C5 acid fluoride -65%. 5.44 g of material collected in the trap To the diglyme residue was added 8.64 g H2O and 1.76 g triethylamine