methyl 2,2,3,3,4,4,4-heptafluorobutanoate

Conditions: temp:-73.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a stirred solution of 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-iodopyrazole (3.0 g) in tetrahydrofuran (80 ml) at -80° C. under an atmosphere of nitrogen was added, at such a rate that the temperature of the reaction mixture did not exceed -73° C., n-butyllithium (2.78 ml of a 2.5M solution in hexanes). The mixture was stirred at -73° C. for 10 minutes and then a solution of methyl heptafluorobutyrate (1.07 ml) in tetrahydrofuran (5 ml) was then added at such a rate that the temperature of the reaction mixture did not exceed -75° C. Upon completion of the addition the mixture allowed to warm to room temperature over a period of 1.5 hours. Water (100 ml) was added and the mixture extracted twice with ethyl acetate (50 ml). The combined organic layers were dried (Na2SO4) and evaporated to give a pale yellow solid which was purified by column chromatography on silica gel (150 g) eluted with ether:hexane (3:2). Combination and evaporation of suitable fractions gave a yellow oil which was further purified by column chromatography on silica gel (150 g) eluted initially with hexane:ether (19:1), then hexane:ether (9:1) and finally hexane:ether (1:1). Combination and evaporation of suitable fractions gave the title compound as a pale yellow solid, m.p. 102-103° C. did not exceed -73° C. did not exceed -75° C Upon completion of the addition the mixture to warm to room temperature over a period of 1.5 hours the mixture extracted twice with ethyl acetate (50 ml) The combined organic layers were dried (Na2SO4) evaporated to give a pale yellow solid which was purified by column chromatography on silica gel (150 g) eluted with ether:hexane (3:2) Combination and evaporation of suitable fractions gave a yellow oil which was further purified by column chromatography on silica gel (150 g) eluted initially with hexane:ether (19:1) Combination and evaporation of suitable fractions

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Where desired, a mixture of water and methylheptafluorobutyrate can be distilled to produce an overhead water/methylheptafluorobutyrate azeotrope. This can be condensed and sufficiently highly cooled to cause phase separation into a light, predominantly aqueous liquid phase and a heavy, predominantly organic liquid phase, and the heavy phase then can be returned to the distillation pot until the water content of the original mixture is substantially exhausted. Temperatures at which the condensate can be cooled can range from about -20° C. to about 75° C., more usually about 0°-30° C., employing any convenient pressure such as atmospheric pressure to maintain substantially liquid phase. can be distilled

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Where desired, a mixture of water and methylheptafluorobutyrate can be distilled to produce an overhead water/methylheptafluorobutyrate azeotrope. This can be condensed and sufficiently highly cooled to cause phase separation into a light, predominantly aqueous liquid phase and a heavy, predominantly organic liquid phase, and the heavy phase then can be returned to the distillation pot until the water content of the original mixture is substantially exhausted. Temperatures at which the condensate can be cooled can range from about -20° C. to about 75° C., more usually about 0°-30° C., employing any convenient pressure such as atmospheric pressure to maintain substantially liquid phase. can be distilled

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Where desired, a mixture of water and methylheptafluorobutyrate can be distilled to produce an overhead water/methylheptafluorobutyrate azeotrope. This can be condensed and sufficiently highly cooled to cause phase separation into a light, predominantly aqueous liquid phase and a heavy, predominantly organic liquid phase, and the heavy phase then can be returned to the distillation pot until the water content of the original mixture is substantially exhausted. Temperatures at which the condensate can be cooled can range from about -20° C. to about 75° C., more usually about 0°-30° C., employing any convenient pressure such as atmospheric pressure to maintain substantially liquid phase. can be distilled

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Following the procedure of E. T. McBee et al. ibid, 2-methyl-3,3,4,4,5,5,5-heptafluoro-pentan-2-ol was prepared by adding methyl heptafluorobutyrate to 2 equivalents of methyl Grignard. The alcohol (boiling point 108° C.) was dehydrated with concentrated sulfuric acid to 2-methyl-3,3,4,4,5,5,5-heptafluoro-pent-1-ene (boiling point 55° C.). Hydrogenation of this olefin at 1500 psig using 5% rhodium/carbon gave 2-methyl-3,3,4,4,5,5,5-heptafluoropentane, boiling point 59°-61° C. 1H NMR (CDCl3)δ 1.2 (d, 6 Hz), 2.45 (m). This compound was miscible with silicone oil with a perfluorinated polyether at 25° C. and with light mineral oil at 56° C.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Following the procedure of E. T. McBee et al. ibid, 2-methyl-3,3,4,4,5,5,5-heptafluoro-pentan-2-ol was prepared by adding methyl heptafluorobutyrate to 2 equivalents of methyl Grignard. The alcohol (boiling point 108° C.) was dehydrated with concentrated sulfuric acid to 2-methyl-3,3,4,4,5,5,5-heptafluoro-pent-1-ene (boiling point 55° C.). Hydrogenation of this olefin at 1500 psig using 5% rhodium/carbon gave 2-methyl-3,3,4,4,5,5,5-heptafluoropentane, boiling point 59°-61° C. 1H NMR (CDCl3)δ 1.2 (d, 6 Hz), 2.45 (m). This compound was miscible with silicone oil with a perfluorinated polyether at 25° C. and with light mineral oil at 56° C.

Conditions: temp:-73.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a stirred solution of 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-iodopyrazole (3.0 g) in tetrahydrofuran (80 ml) at -80° C. under an atmosphere of nitrogen was added, at such a rate that the temperature of the reaction mixture did not exceed -73° C., n-butyllithium (2.78 ml of a 2.5M solution in hexanes). The mixture was stirred at -73° C. for 10 minutes and then a solution of methyl heptafluorobutyrate (1.07 ml) in tetrahydrofuran (5 ml) was then added at such a rate that the temperature of the reaction mixture did not exceed -75° C. Upon completion of the addition the mixture allowed to warm to room temperature over a period of 1.5 hours. Water (100 ml) was added and the mixture extracted twice with ethyl acetate (50 ml). The combined organic layers were dried (Na2SO4) and evaporated to give a pale yellow solid which was purified by column chromatography on silica gel (150 g) eluted with ether:hexane (3:2). Combination and evaporation of suitable fractions gave a yellow oil which was further purified by column chromatography on silica gel (150 g) eluted initially with hexane:ether (19:1), then hexane:ether (9:1) and finally hexane:ether (1:1). Combination and evaporation of suitable fractions gave the title compound as a pale yellow solid, m.p. 102-103° C. did not exceed -73° C. did not exceed -75° C Upon completion of the addition the mixture to warm to room temperature over a period of 1.5 hours the mixture extracted twice with ethyl acetate (50 ml) The combined organic layers were dried (Na2SO4) evaporated to give a pale yellow solid which was purified by column chromatography on silica gel (150 g) eluted with ether:hexane (3:2) Combination and evaporation of suitable fractions gave a yellow oil which was further purified by column chromatography on silica gel (150 g) eluted initially with hexane:ether (19:1) Combination and evaporation of suitable fractions

Conditions: temp:-73.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a stirred solution of 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-iodopyrazole (3.0 g) in tetrahydrofuran (80 ml) at -80° C. under an atmosphere of nitrogen was added, at such a rate that the temperature of the reaction mixture did not exceed -73° C., n-butyllithium (2.78 ml of a 2.5M solution in hexanes). The mixture was stirred at -73° C. for 10 minutes and then a solution of methyl heptafluorobutyrate (1.07 ml) in tetrahydrofuran (5 ml) was then added at such a rate that the temperature of the reaction mixture did not exceed -75° C. Upon completion of the addition the mixture allowed to warm to room temperature over a period of 1.5 hours. Water (100 ml) was added and the mixture extracted twice with ethyl acetate (50 ml). The combined organic layers were dried (Na2SO4) and evaporated to give a pale yellow solid which was purified by column chromatography on silica gel (150 g) eluted with ether:hexane (3:2). Combination and evaporation of suitable fractions gave a yellow oil which was further purified by column chromatography on silica gel (150 g) eluted initially with hexane:ether (19:1), then hexane:ether (9:1) and finally hexane:ether (1:1). Combination and evaporation of suitable fractions gave the title compound as a pale yellow solid, m.p. 102-103° C. did not exceed -73° C. did not exceed -75° C Upon completion of the addition the mixture to warm to room temperature over a period of 1.5 hours the mixture extracted twice with ethyl acetate (50 ml) The combined organic layers were dried (Na2SO4) evaporated to give a pale yellow solid which was purified by column chromatography on silica gel (150 g) eluted with ether:hexane (3:2) Combination and evaporation of suitable fractions gave a yellow oil which was further purified by column chromatography on silica gel (150 g) eluted initially with hexane:ether (19:1) Combination and evaporation of suitable fractions

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Where desired, a mixture of water and methylheptafluorobutyrate can be distilled to produce an overhead water/methylheptafluorobutyrate azeotrope. This can be condensed and sufficiently highly cooled to cause phase separation into a light, predominantly aqueous liquid phase and a heavy, predominantly organic liquid phase, and the heavy phase then can be returned to the distillation pot until the water content of the original mixture is substantially exhausted. Temperatures at which the condensate can be cooled can range from about -20° C. to about 75° C., more usually about 0°-30° C., employing any convenient pressure such as atmospheric pressure to maintain substantially liquid phase. can be distilled

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Where desired, a mixture of water and methylheptafluorobutyrate can be distilled to produce an overhead water/methylheptafluorobutyrate azeotrope. This can be condensed and sufficiently highly cooled to cause phase separation into a light, predominantly aqueous liquid phase and a heavy, predominantly organic liquid phase, and the heavy phase then can be returned to the distillation pot until the water content of the original mixture is substantially exhausted. Temperatures at which the condensate can be cooled can range from about -20° C. to about 75° C., more usually about 0°-30° C., employing any convenient pressure such as atmospheric pressure to maintain substantially liquid phase. can be distilled

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Methyl perfluorobutyrate (12.81 g, 56 mmol) was added dropwise to a stirred solution of sodium trimethylsilanolate (6.3 g, 56 mmol) in dry ether (300 mL) at room temperature under nitrogen. The reaction mixture was stirred overnight. The solid was filtered under nitrogen, washed with dry ether, and dried under a stream of nitrogen to afford sodium perfluorobutyrate (11.1 g, 84% yield) as a white solid: 19F NMR (D2O) δ -79.6 (t, J=8 Hz, CF3 --, 3F), -117.2 (q, J=8 Hz, CF3CF2CF2 --, 2F), -126.2 ppm (s, CF3CF2 --, 2F). Anal. Calcd. for C4F7NaO2 : C, 20.36; F, 56.35; Na, 9.74. Found: C, 20.84, 20.61, 20.58; F, 56.68, 53.24; Na, 9.89, 9.65. The solid was filtered under nitrogen washed with dry ether dried under a stream of nitrogen

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Where desired, a mixture of water and methylheptafluorobutyrate can be distilled to produce an overhead water/methylheptafluorobutyrate azeotrope. This can be condensed and sufficiently highly cooled to cause phase separation into a light, predominantly aqueous liquid phase and a heavy, predominantly organic liquid phase, and the heavy phase then can be returned to the distillation pot until the water content of the original mixture is substantially exhausted. Temperatures at which the condensate can be cooled can range from about -20° C. to about 75° C., more usually about 0°-30° C., employing any convenient pressure such as atmospheric pressure to maintain substantially liquid phase. can be distilled