2-氯乙基 2,2,2-三氟乙酸酯

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A mixture of 29.1 g (0.50 mol) of dry potassium fluoride' 88.3 g (0.50 mol) of 2-chloroethyl trifluoroacetate, 150 mL of dimethylsulfoxide, and 50 g (0.50 mol) of tetrafluoroethylene was shaken in a 400-mL metal tube at 75° for 18 h. Volatile products were transferred from the reaction mixture held at 43° (1.2 mm). These volatiles were stirred with 500 mL of 10% aqueous NaOH to remove unreacted ester and a small amount of dimethylsulfoxide, then fractionated to afford 61.6 g (47%) of 2-trifluoromethyl-2-pentafluoroethyl-1,3-dioxolane, b.p. 118°-120° . IR (CCl4) and NMR (CCl4) spectra for the product were consistent with the assigned structure. Anal.: Calcd. for C6H4F8O2 : C, 27.71; H, 1.55; F, 58.44. Found: C, 27.57; H, 1.65; F, 58.40. held at 43° to remove unreacted ester

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A suspension of 12.0 g (0.25 mol) of 50 % NaH in mineral oil in 100 mL of dry diglyme (diethylene glycol dimethyl ether) was stirred at 25° under nitrogen while a solution of 23.5 g (0.25 mol) of phenol in 50 mL of diglyme was added. The resulting mixture was stirred until evolution of gas ceased, then charged into a 400 mL metal tube along with 44.3 g (0.25 mol) of 2-chloroethyl trifluoroacetate and 40 g (0.70 mol) of tetrafluoroethylene. The resulting mixture was agitated for 6 h while the temperature rose to 34° and subsided. Next the mixture was heated at 50° for 6 h. The resulting reaction mixture was added to L of water, thereby causing the formation of layers. The lower layer was separated, washed with water, dried over CaSO4, and distilled to give 61.2 g (73% yield) of 2-trifluoromethyl-2(2-phenoxytetrafluoroethyl)-1,3-dioxolane, b.p. 64°-67° at 13 Pa (0.1 mm). The IR (CCl4) and NMR (CC14) spectra of the product were consistent with the structure assignment. Anal.: Calcd. for C12H9F7O3 :C,43.13; H, 2.71; F, 39.80. Found: C, 43.23; H, 2.75; F, 39.90. was added The resulting mixture was agitated for 6 h while the temperature rose to 34° Next the mixture was heated at 50° for 6 h The resulting reaction mixture The lower layer was separated washed with water dried over CaSO4 distilled

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of 23.5 g (0.25 mol) of phenol in 50 mL of DMSO was added dropwise to a stirred suspension of 12.0 g (0.25 mol) of 50% NaH in mineral oil in 100 mL of DMSO maintained at 15°-20° by cooling. After evolution of gas had slowed, cooling and stirring were continued while 44.3 g (0.25 mol) of 2-chloroethyl trifluoroacetate were added. The temperature of the reaction mixture was kept below 30° while the exotherm which occurred subsided, then the resulting mixture was stirred overnight, poured into 1 L of water, and extracted with 200 mL, then two 100 mL portions, of ether. The resulting ether solutions were washed with water, dried over CaSO4, and distilled to give 27.6 g (47% yield) of 2-phenoxy-2-trifluoromethyl-1,3-dioxolane, b.p. 52°-54° at 80 Pa (0.6 mm). IR (neat) and NMR (CCl4) spectra were consistent with the assigned structure. maintained at 15°-20° by cooling cooling were added was kept below 30° while the exotherm which the resulting mixture was stirred overnight extracted with 200 mL The resulting ether solutions were washed with water dried over CaSO4 distilled

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: This example illustrates a process of the invention only. A suspension of 9.6 g (0.20 mol) of 50% NaH in mineral oil in 150 mL of DM$0 was stirred at 15°-20° while 35.4 g (0.20 mol) of 2-chloroethyl trifluoroacetate were added dropwise. The resulting mixture was stirred overnight while the reaction temperature was maintained below 30° . The reaction mixture was then heated to 50° at 0.33 kPa (2.5 mm) to drive off volatile products which were recovered. Fractionation of the volatiles gave 8.5 g (30% yield) of 2-trifluoromethyl-1,3-dioxolane, b.p. 87°-93° . IR (CCl4): 3000 and 2910 (sat'd CH), 1200-1100 cm-1 (CF,C--O). NMR (CCl4): 1H 5.13 (q, JHF 4Hz, IH, CH) and 4.07 ppm (s, 4H, ring OCH2). Anal.: Calcd. for C4H5F3O2 : C, 33.81; H, 3.55. Found: C, 33.68; H, 3.39 were added dropwise was maintained below 30° The reaction mixture was then heated to 50° at 0.33 kPa (2.5 mm) were recovered

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A suspension of 5.4 g (0.10 mol) of sodium methoxide in 50 mL of tetrahydrofuran (THF) was stirred at -20° to -10° while 17.7 g (0.10 mol) of 2-chloroethyl trifluoroacetate were added dropwise. The resulting clear solution was allowed to warm with precipitation commencing at about 10° and a slow exotherm ensuing to 35° . The mixture was maintain below 35° until the exotherm subsided and then was stirred for 4 h. Filtration and fractionation of the filtrate gave 7.4 g (43% yield) of 2-methoxy-2-trifluoromethyl-1,3-dioxolane, b.p. 61°-62° at 3.3 kPa (25 mm). IR (neat): 3000, 2965, 3 2925, and 2680 (sat,d CH), 1250-1100 cm-1 (CF, C--0). NMR (CCl4): 1H 4.17 (m, 4H, ring CH2 and 3.33 ppm (s, 3H, OCH3); 19 F-85.0 ppm (s, CF3). were added dropwise to warm with precipitation commencing at about 10° ensuing to 35° The mixture was maintain below 35° until the exotherm Filtration and fractionation of the filtrate

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A mixture of 29.1 g (0.50 mol) of dry potassium fluoride, 88.3 g (0.50 mol) of 2-chloroethyl trifluoroacetate, 150 mL of dimethylsulfoxide, and 50 g (0.50 mol) of tetrafluoroethylene was shaken in a 400-mL metal tube at 75° for 18 h. Volatile products were transferred from the reaction mixture held at 43° (1.2 mm). These volatiles were stirred with 500 mL of 10% aqueous NaOH to remove unreacted ester and a small amount of dimethylsulfoxide, then fractionated to afford 61.6 g (47%) of 2-trifluoromethyl-2-pentafluoroethyl-1,3-dioxolane, b.p. 118°-120°. IR (CCl4) and NMR (CCl4) spectra for the product were consistent with the assigned structure. Anal.: Calcd. for C6H4F8O2 : C, 27.71; H, 1.55; F, 58.44. Found: C, 27.57; H, 1.65; F, 58.40. held at 43° to remove unreacted ester

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A suspension of 12.0 g (0.25 mol) of 50 % NaH in mineral oil in 100 mL of dry diglyme (diethylene glycol dimethyl ether) was stirred at 25° under nitrogen while a solution of 23.5 g (0.25 mol) of phenol in 50 mL of diglyme was added. The resulting mixture was stirred until evolution of gas ceased, then charged into a 400 mL metal tube along with 44.3 g (0.25 mol) of 2-chloroethyl trifluoroacetate and 40 g (0.70 mol) of tetrafluoroethylene. The resulting mixture was agitated for 6 h while the temperature rose to 34° and subsided. Next the mixture was heated at 50 ° for 6 h. The resulting reaction mixture was added to 1 L of water, thereby causing the formation of layers. The lower layer was separated, washed with water, dried over CaSO4, and distilled to give 61.2 g (73% yield) of 2-trifluoromethyl-2-(2-phenoxytetrafluoroethyl)-1,3-dioxolane, b.p. 64°-67° at 13 Pa (0.1 mm). The IR (CCl4) and NMR (CCl4) spectra of the product were consistent with the structure assignment. Anal.: Calcd. for C12H9F7O3 : C, 43.13; H, 2.71; F, 39.80. Found: C, 43.23; H, 2.75; F, 39.90. was added The resulting mixture was agitated for 6 h while the temperature rose to 34° Next the mixture was heated at 50 ° for 6 h The resulting reaction mixture The lower layer was separated washed with water dried over CaSO4 distilled

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of 23.5 g (0.25 mol) of phenol in 50 mL of DMSO was added dropwise to a stirred suspension of 12.0 g (0.25 mol) of 50% NaH in mineral oil in 100 mL of DMSO maintained at 15°-20° by cooling. After evolution of gas had slowed, cooling and stirring were continued while 44.3 g (0.25 mol) of 2-chloroethyl trifluoroacetate were added. The temperature of the reaction mixture was kept below 30° while the exotherm which occurred subsided, then the resulting mixture was stirred overnight, poured into 1 L of water, and extracted with 200 mL, then two 100 mL portions, of ether. The resulting ether solutions were washed with water, dried over CaSO4, and distilled to give 27.6 g (47% yield) of 2-phenoxy-2-trifluoromethyl-1,3-dioxolane, b.p. 52°-54° at 80 Pa (0.6 mm). IR (neat) and NMR (CCl4) spectra were consistent with the assigned structure maintained at 15°-20° by cooling cooling were added was kept below 30° while the exotherm which the resulting mixture was stirred overnight extracted with 200 mL The resulting ether solutions were washed with water dried over CaSO4 distilled

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: This example illustrates a process of the invention only. A suspension of 9.6 g (0.20 mol) of 50% NaH in mineral oil in 150 mL of DMSO was stirred at 15°-20° while 35.4 g (0.20 mol) of 2-chloroethyl trifluoroacetate were added dropwise. The resulting mixture was stirred overnight while the reaction temperature was maintained below 30°. The reaction mixture was then heated to 50° at 0.33 kPa (2.5 mm) to drive off volatile products which were recovered. Fractionation of the volatiles gave 8.5 g (30% yield) of 2-trifluoromethyl-1,3-dioxolane, b.p. 87°-93°. IR (CCl4): 3000 and 2910 (sat'd CH), 1200-1100 cm-1 (CF, C--O). NMR (CCl4): 1H 5.13 (q, JHF 4Hz, 1H, CH) and 4.07 ppm (s, 4H, ring OCH2). Anal.: Calcd. for C4H5F3O2 : C, 33.81; H, 3.55. Found: C, 33.68; H, 3.39 were added dropwise was maintained below 30° The reaction mixture was then heated to 50° at 0.33 kPa (2.5 mm) were recovered

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: This example illustrates a process of the invention only. A suspension of 9.6 g (0.20 mol) of 50% NaH in mineral oil in 150 mL of DMSO was stirred at 15°-20° while 35.4 g (0.20 mol) of 2-chloroethyl trifluoroacetate were added dropwise. The resulting mixture was stirred overnight while the reaction temperature was maintained below 30°. The reaction mixture was then heated to 50° at 0.33 kPa (2.5 mm) to drive off volatile products which were recovered. Fractionation of the volatiles gave 8.5 g (30% yield) of 2-trifluoromethyl-1,3-dioxolane, b.p. 87°-93°. IR (CCl4): 3000 and 2910 (sat'd CH), 1200-1100 cm-1 (CF, C--O). NMR (CCl4): 1H 5.13 (q, JHF 4Hz, 1H, CH) and 4.07 ppm (s, 4H, ring OCH2). Anal.: Calcd. for C4H5F3O2 : C, 33.81; H, 3.55. Found: C, 33.68; H, 3.39 were added dropwise was maintained below 30° The reaction mixture was then heated to 50° at 0.33 kPa (2.5 mm) were recovered

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A suspension of 5.4 g (0.10 mol) of sodium methoxide in 50 mL of tetrahydrofuran (THF) was stirred at -20° to -10° while 17.7 g (0.10 mol) of 2-chloroethyl trifluoroacetate were added dropwise. The resulting clear solution was allowed to warm with precipitation commencing at about 10° and a slow exotherm ensuing to 35°. The mixture was maintain below 35° until the exotherm subsided and then was stirred for 4 h. Filtration and fractionation of the filtrate gave 7.4 g (43% yield) of 2-methoxy-2-trifluoromethyl-1,3-dioxolane, b.p. 61°-62° at 3.3 kPa (25 mm). IR (neat): 3000, 2965, 2925, and 2680 (sat'd CH), 1250-1100 cm-1 (CF, C--O). NMR (CCl4): 1H 4.17 (m, 4H, ring CH2 and 3.33 ppm (s, 3H, OCH3); 19 F-85.0 ppm (s, CF3). were added dropwise to warm with precipitation commencing at about 10° ensuing to 35° The mixture was maintain below 35° until the exotherm Filtration and fractionation of the filtrate