fluoro(trimethyl)silane

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

Procedure: Example 8 was repeated using the same reactor and catalyst/support charge. CF3CF2CF2OCF(CF3)CO2SiMe3 (128.6 g, 0.320 mmol) was added dropwise at ca. 20 g/hr using N2 carrier flow of 34 mL/min. There was obtained 109.1 g of liquid product consisting of PPVE (49.4 mole %), TMSF (48.4%) and C3F7OCHFCF3 (2.2%). Distillation using a 24" spinning band column gave 23.9 g of an azeotrope (74/26 TMSF/PPVE by weight), 23.5 g of intermediate fractions, and 51.6 g of >99.8% purity PPVE. Distillation

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

Procedure: Example 8 was repeated using the same reactor and catalyst/support charge. CF3CF2CF2OCF(CF3)CO2SiMe3 (16.20 g, 40.3 mmol) was added dropwise over 1.5 hr. There was obtained 13.94 g of liquid product consisting of an equimolar mixture of PPVE and TMSF. Less than 0.2% starting TMS ester remained, and less than 1% C3F7OCHFCF3 was produced.

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

Procedure: Example 8 was repeated using the same reactor and catalyst/support charge. CF3CF2CF2OCF(CF3)CO2SiMe3 (128.6 g, 0.320 mmol) was added dropwise at ca. 20 g/hr using N2 carrier flow of 34 mL/min. There was obtained 109.1 g of liquid product consisting of PPVE (49.4 mole %), TMSF (48.4%) and C3F7OCHFCF3 (2.2%). Distillation using a 24" spinning band column gave 23.9 g of an azeotrope (74/26 TMSF/PPVE by weight), 23.5 g of intermediate fractions, and 51.6 g of >99.8% purity PPVE. Distillation

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

Procedure: Example 8 was repeated using the same reactor and catalyst/support charge. CF3CF2CF2OCF(CF3)CO2SiMe3 (128.6 g, 0.320 mmol) was added dropwise at ca. 20 g/hr using N2 carrier flow of 34 mL/min. There was obtained 109.1 g of liquid product consisting of PPVE (49.4 mole %), TMSF (48.4%) and C3F7OCHFCF3 (2.2%). Distillation using a 24" spinning band column gave 23.9 g of an azeotrope (74/26 TMSF/PPVE by weight), 23.5 g of intermediate fractions, and 51.6 g of >99.8% purity PPVE. Distillation

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

Procedure: Example 8 was repeated using the same reactor and catalyst/support charge. CF3CF2CF2OCF(CF3)CO2SiMe3 (16.20 g, 40.3 mmol) was added dropwise over 1.5 hr. There was obtained 13.94 g of liquid product consisting of an equimolar mixture of PPVE and TMSF. Less than 0.2% starting TMS ester remained, and less than 1% C3F7OCHFCF3 was produced.

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

Procedure: Example 8 was repeated using the same reactor and catalyst/support charge. CF3CF2CF2OCF(CF3)CO2SiMe3 (16.20 g, 40.3 mmol) was added dropwise over 1.5 hr. There was obtained 13.94 g of liquid product consisting of an equimolar mixture of PPVE and TMSF. Less than 0.2% starting TMS ester remained, and less than 1% C3F7OCHFCF3 was produced.

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

Procedure: Bromine, 17.25 g (0.108 mol), was added dropwise at 0° to a solution of tris(dimethylamino)sulfonium 1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)-2-propanide, prepared by dissolving 33.4 g (0.12 mol) of tri(dimethylamino)sulfonium difluorotrimethylsilicate and 24.0 g (0.12 mol) of perfluoroisobutylene in 75 mL of benzonitrile, then pumping out the by-product fluorotrimethylsilane at reduced pressure. The reaction mixture was evacuated to transfer the volatile reaction product into a cold trap (-78°). Sublimation of the contents of the trap at atmospheric pressure gave 26.11 g (81%) of 2-bromo-1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)propane as a very volatile solid: m.p. (sublimation 49°-51°; 19F NMR (CDCl3) δ -67.6 ppm (s). prepared The reaction mixture was evacuated (-78°)

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

Procedure: Bromine, 17.25 g (0.108 mol), was added dropwise at 0° to a solution of tris(dimethylamino)sulfonium 1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)-2-propanide, prepared by dissolving 33.4 g (0.12 mol) of tri(dimethylamino)sulfonium difluorotrimethylsilicate and 24.0 g (0.12 mol) of perfluoroisobutylene in 75 mL of benzonitrile, then pumping out the by-product fluorotrimethylsilane at reduced pressure. The reaction mixture was evacuated to transfer the volatile reaction product into a cold trap (-78°). Sublimation of the contents of the trap at atmospheric pressure gave 26.11 g (81%) of 2-bromo-1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)propane as a very volatile solid: m.p. (sublimation 49°-51°; 19F NMR (CDCl3) δ -67.6 ppm (s). prepared The reaction mixture was evacuated (-78°)

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

Procedure: Example 8 was repeated using the same reactor and catalyst/support charge. CF3CF2CF2OCF(CF3)CO2SiMe3 (128.6 g, 0.320 mmol) was added dropwise at ca. 20 g/hr using N2 carrier flow of 34 mL/min. There was obtained 109.1 g of liquid product consisting of PPVE (49.4 mole %), TMSF (48.4%) and C3F7OCHFCF3 (2.2%). Distillation using a 24" spinning band column gave 23.9 g of an azeotrope (74/26 TMSF/PPVE by weight), 23.5 g of intermediate fractions, and 51.6 g of >99.8% purity PPVE. Distillation

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

Procedure: Example 8 was repeated using the same reactor and catalyst/support charge. CF3CF2CF2OCF(CF3)CO2SiMe3 (128.6 g, 0.320 mmol) was added dropwise at ca. 20 g/hr using N2 carrier flow of 34 mL/min. There was obtained 109.1 g of liquid product consisting of PPVE (49.4 mole %), TMSF (48.4%) and C3F7OCHFCF3 (2.2%). Distillation using a 24" spinning band column gave 23.9 g of an azeotrope (74/26 TMSF/PPVE by weight), 23.5 g of intermediate fractions, and 51.6 g of >99.8% purity PPVE. Distillation

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

Procedure: Example 8 was repeated using the same reactor and catalyst/support charge. CF3CF2CF2OCF(CF3)CO2SiMe3 (16.20 g, 40.3 mmol) was added dropwise over 1.5 hr. There was obtained 13.94 g of liquid product consisting of an equimolar mixture of PPVE and TMSF. Less than 0.2% starting TMS ester remained, and less than 1% C3F7OCHFCF3 was produced.

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

Procedure: Example 8 was repeated using the same reactor and catalyst/support charge. CF3CF2CF2OCF(CF3)CO2SiMe3 (16.20 g, 40.3 mmol) was added dropwise over 1.5 hr. There was obtained 13.94 g of liquid product consisting of an equimolar mixture of PPVE and TMSF. Less than 0.2% starting TMS ester remained, and less than 1% C3F7OCHFCF3 was produced.