1,2-dichloro-1,2-difluoroethene

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: In a 500 ml stirred reaction flask equipped with thermometer, air condenser, dropping funnel and ice water bath was placed 94 g (one mole) of phenol and 300 ml of acetone and the mixture was cooled to 10° C. 11.0 Grams of powdered KOH (85 percent) was then added. After the mixture was stirred for one-half hour at 10° C., 2,2-dichloro-1,1-difluoroethene was introduced over a period of one hour while maintaining the temperature at about 10-12° C. At the end of the addition of the dichlorodifluoroethene, a rapid reaction increased the temperature to 50° C. A Dry Ice(R) bath was substituted for the ice bath to cool the reaction mixture to 10° C. rapidly. After stirring overnight, the reaction mixture was poured over two liters of ice, stirred, allowed to settle and the oil layer was separated. The oil layer was washed with bicarbonate of soda solution and with water and the nearly colorless organic layer was separated. After drying over desiccant-grade magnesium sulfate, the organic layer was filtered to give the first-step product. reaction flask equipped with thermometer, air condenser After the mixture was stirred for one-half hour at 10° C. while maintaining the temperature at about 10-12° C a rapid reaction increased the temperature to 50° C to cool the reaction mixture to 10° C. rapidly After stirring overnight stirred the oil layer was separated The oil layer was washed with bicarbonate of soda solution and with water the nearly colorless organic layer was separated After drying over desiccant-grade magnesium sulfate the organic layer was filtered to give the first-step product

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: Chlorofluoronitroacetic Acid, Oleum-Trifluoroacetic Acid Procedure. A solution of 100% nitric acid (5 mL) and trifluoroacetic acid (4.2 mL, 54 mmol) in 30% oleum (6 mL) was added over 25 min to 1,2-dichlorodifluoroethylene (7.5 g, 56 mmol) at 10°-15° C. The mixture was stirred for 60 min at 10°-14° C. The organic layer was separated, and fractionally distilled to give 2.1 g (14.5%) of 1,2-dichloro-1,2-difluoro-1-nitroethyl trifluoroacetate, as a 50:50 mixture of diasterimers, bp 48°-50° C. (0.5 mm): 19F NMR (CDCl3 ) δ -76.27 (s, 6 F), -77.50 (s,1 F), -78.49 (s, 1F), -94.37 (s, 1 F), -95.30 (s, 1 F). The second fraction contained 4.0 g of chlorofluoronitroacetic acid, bp 55°-65° C. (0.5 mm), identical to the authentic material prepared above. The oleum layer was heated to 80° C. under vacuum (0.5 mm) to give an additional 1.61 g (63% combined yield) of chlorofluoronitroacetic acid. The organic layer was separated fractionally distilled

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

実験手順: Chlorofluoronitroacetic Acid, Oleum-Trifluoroacetic Acid Procedure. A solution of 100% nitric acid (5 mL) and trifluoroacetic acid (4.2 mL, 54 mmol) in 30% oleum (6 mL) was added over 25 min to 1,2-dichlorodifluoroethylene (7.5 g, 56 mmol) at 10°-15° C. The mixture was stirred for 60 min at 10°-14° C. The organic layer was separated, and fractionally distilled to give 2.1 g (14.5%) of 1,2-dichloro-1,2-difluoro-1-nitroethyl trifluoroacetate, as a 50:50 mixture of diasterimers, bp 48°-50° C. (0.5 mm): 19F NMR (CDCl3 ) δ -76.27 (s, 6 F), -77.50 (s,1 F), -78.49 (s, 1F), -94.37 (s, 1 F), -95.30 (s, 1 F). The second fraction contained 4.0 g of chlorofluoronitroacetic acid, bp 55°-65° C. (0.5 mm), identical to the authentic material prepared above. The oleum layer was heated to 80° C. under vacuum (0.5 mm) to give an additional 1.61 g (63% combined yield) of chlorofluoronitroacetic acid. The organic layer was separated fractionally distilled

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

実験手順: The yield of chlorofluoronitroacetic acid in the nitration reaction was increased to 44% by replacing sulfuric acid with oleum. When a mixture of oleum, nitric acid and trifluoracetic acid was reacted with 1,2-dichlorodifluoroethylene, chlorofluoronitroacetic acid was obtained in 63% yield along with 14% of the 1,2-addition product, 1,2-dichloro-1,2-difluoro-2-nitroethyl trifluoroacetate, bringing the total yield of the nitration reaction to 77%. Apparently the 1,2-addition product was formed first and then was hydrolyzed in situ, to give the acetic acid derivative. The lower boiling point and diminished water sensitivity of the 1,2-addition product makes it a potentially attractive alternative to chlorofluoronitroacetic acid in subsequent nitration reactions. was increased to 44%

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

実験手順: The yield of chlorofluoronitroacetic acid in the nitration reaction was increased to 44% by replacing sulfuric acid with oleum. When a mixture of oleum, nitric acid and trifluoracetic acid was reacted with 1,2-dichlorodifluoroethylene, chlorofluoronitroacetic acid was obtained in 63% yield along with 14% of the 1,2-addition product, 1,2-dichloro-1,2-difluoro-2-nitroethyl trifluoroacetate, bringing the total yield of the nitration reaction to 77%. Apparently the 1,2-addition product was formed first and then was hydrolyzed in situ, to give the acetic acid derivative. The lower boiling point and diminished water sensitivity of the 1,2-addition product makes it a potentially attractive alternative to chlorofluoronitroacetic acid in subsequent nitration reactions. was increased to 44%

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

実験手順: a process wherein trichlorofluoromethane is added to 1,2-dichlorodifluoroethylene or carbon tetrachloride is added to chlorotrifluoroethylene to obtain 1,1,2-trifluoropentachloropropane, which is then oxidized and esterified to form a 2,3-dichlorotrifluoropropionic acid ester, followed by dechlorination of the ester; (2) a process wherein bromine is added to chlorotrifluoroethylene to obtain 1,2-dibromo-1-chlorotrifluoroethylene, which is then subjected to an addition reaction with propylene, followed by dehydrobromination to obtain 5-bromo-4-chloro-4,5,5-trifluoropentene-2 (CF2BrCFClCH=CHCH3), which is then oxidized and esterified to form a 3-bromo-2-chlorotrifluoropropionic acid ester, which is in turn dehalogenated; and (3) a process wherein chlorotrifluoroethylene is subjected to an addition reaction with hydrogen bromide, followed by dehalogenation to obtain trifluoroethylene, which is then subjected to an addition reaction with ICl, followed by dehydrochlorination to obtain trifluoroiodoethylene, which is then reacted with metallic magnesium in ether to form an organomagnesium intermediate, which is in turn reacted with carbon dioxide, followed by hydrolysis to obtain perfluoroacrylic acid, which is then esterified.