1,1,1-trifluoro-2-(trifluoromethyl)pent-4-en-2-ol

Conditions: temp:190.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 500 ml autoclave was charged with 230 g of 1,1-bis(trifluoromethyl)-3-butenol, 73 g of dicyclopentadiene, and 0.15 g of 2,6-di-t-butylparacresol, and the mixture was heated at 190° C. for 12 hours. The reaction solution was cooled to room temperature and purified by distillation to obtain 40 g of 8-(2,2,2-trifluoro-1-trifluoromethyl-1-hydroxyethyl)tetracyclo[4.4.0.12,5.17,10]dodec-3-ene of the following formula (13). The reaction solution was cooled to room temperature purified by distillation

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

Procedure: 19 g of sodium styrenesulfonate (SSNa) (available from Sigma-Aldrich Corp.) and 1 g of 2-Allylhexafluoro-isopropanol are fully dissolved in 0.24 L of dimethylsulfoxide (DMSO) with heating. Then, 0.1 g of azobisisobutyronitrile (AIBN) is added dropwise to the DMSO solution. The monomers are polymerized for 24 hours or more. The polymerization is carried out varying the content of the allylhexafluoro-isopropanol (2, 5, 10, and 20 wt %). with heating The monomers are polymerized for 24 hours or more

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

Procedure: 19 g of sodium styrenesulfonate (SSNa) (available from Sigma-Aldrich Corp.) and 1 g of 2-Allylhexafluoro-isopropanol are fully dissolved in 0.24 L of dimethylsulfoxide (DMSO) with heating. Then, 0.1 g of azobisisobutyronitrile (AIBN) is added dropwise to the DMSO solution. The monomers are polymerized for 24 hours or more. The polymerization is carried out varying the content of the allylhexafluoro-isopropanol (2, 5, 10, and 20 wt %). with heating The monomers are polymerized for 24 hours or more

Conditions: temp:190.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 500 ml autoclave was charged with 230 g of 1,1-bis(trifluoromethyl)-3-butenol, 73 g of dicyclopentadiene, and 0.15 g of 2,6-di-t-butylparacresol, and the mixture was heated at 190° C. for 12 hours. The reaction solution was cooled to room temperature and purified by distillation to obtain 40 g of 8-(2,2,2-trifluoro-1-trifluoromethyl-1-hydroxyethyl)tetracyclo[4.4.0.12,5.17,10]dodec-3-ene of the following formula (13). The reaction solution was cooled to room temperature purified by distillation

Conditions: temp:190.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 500 ml autoclave was charged with 230 g of 1,1-bis(trifluoromethyl)-3-butenol, 73 g of dicyclopentadiene, and 0.15 g of 2,6-di-t-butylparacresol, and the mixture was heated at 190° C. for 12 hours. The reaction solution was cooled to room temperature and purified by distillation to obtain 40 g of 8-(2,2,2-trifluoro-1-trifluoromethyl-1-hydroxyethyl)tetracyclo[4.4.0.12,5.17,10]dodec-3-ene of the following formula (13). The reaction solution was cooled to room temperature purified by distillation

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

Procedure: To a 250 mL 3 neck roundbottom flask with reflux condenser and Teflon-coated magnetic stir bar was added methyl acrylate (9.10 g, 105.7 mmol, 1.1 eq.), 1,1,1-trifluoro-2-trifluoromethyl-pent-4-ene-2-ol (20 g, 96.1 mmol, 1 eq.) and 100 mL of anhydrous dichloromethane. The solution was heated to reflux under nitrogen and 300 mg of the Hoveyda-Grubbs 2nd generation ruthenium metathesis catalyst (0.048 mmol, 0.005 eq.) was added in 4 portions over 4 hours. The reaction was heated an additional 12 hours after which the product was purified by vacuum distillation (65° C., 6 Torr) and column chromatography (silica gel, 80:20 hexane:ethyl acetate eluent) to afford 16.7 g of methyl 6,6,6-trifluoro-5-hydroxy-5-(trifluoromethyl)hex-2-enoate (I) as colorless liquid (E/Z=2.15:1) contaminated with a small amount (0.15 eq.) of 1,1,1,8,8,8-hexafluoro-2,7-di(trifluoromethyl)-oct-4-ene-2,7-diol (E/Z=6.7:1). The solution was heated to reflux under nitrogen The reaction was heated an additional 12 hours after which the product was purified by vacuum distillation (65° C., 6 Torr) and column chromatography (silica gel, 80:20 hexane:ethyl acetate eluent)

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

Procedure: To a 250 mL 3 neck roundbottom flask with reflux condenser and Teflon-coated magnetic stir bar was added methyl acrylate (9.10 g, 105.7 mmol, 1.1 eq.), 1,1,1-trifluoro-2-trifluoromethyl-pent-4-ene-2-ol (20 g, 96.1 mmol, 1 eq.) and 100 mL of anhydrous dichloromethane. The solution was heated to reflux under nitrogen and 300 mg of the Hoveyda-Grubbs 2nd generation ruthenium metathesis catalyst (0.048 mmol, 0.005 eq.) was added in 4 portions over 4 hours. The reaction was heated an additional 12 hours after which the product was purified by vacuum distillation (65° C., 6 Torr) and column chromatography (silica gel, 80:20 hexane:ethyl acetate eluent) to afford 16.7 g of methyl 6,6,6-trifluoro-5-hydroxy-5-(trifluoromethyl)hex-2-enoate (I) as colorless liquid (E/Z=2.15:1) contaminated with a small amount (0.15 eq.) of 1,1,1,8,8,8-hexafluoro-2,7-di(trifluoromethyl)-oct-4-ene-2,7-diol (E/Z=6.7:1). The solution was heated to reflux under nitrogen The reaction was heated an additional 12 hours after which the product was purified by vacuum distillation (65° C., 6 Torr) and column chromatography (silica gel, 80:20 hexane:ethyl acetate eluent)

Conditions: temp:190.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 500 ml autoclave was charged with 230 g of 1,1-bis(trifluoromethyl)-3-butenol, 73 g of dicyclopentadiene, and 0.15 g of 2,6-di-t-butylparacresol, and the mixture was heated at 190° C. for 12 hours. The reaction solution was cooled to room temperature and purified by distillation to obtain 40 g of 8-(2,2,2-trifluoro-1-trifluoromethyl-1-hydroxyethyl)tetracyclo[4.4.0.12,5.17,10]dodec-3-ene of the following formula (13). The reaction solution was cooled to room temperature purified by distillation

Conditions: temp:190.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 500 ml autoclave was charged with 230 g of 1,1-bis(trifluoromethyl)-3-butenol, 73 g of dicyclopentadiene, and 0.15 g of 2,6-di-t-butylparacresol, and the mixture was heated at 190° C. for 12 hours. The reaction solution was cooled to room temperature and purified by distillation to obtain 40 g of 8-(2,2,2-trifluoro-1-trifluoromethyl-1-hydroxyethyl)tetracyclo[4.4.0.12,5.17,10]dodec-3-ene of the following formula (13). The reaction solution was cooled to room temperature purified by distillation

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

Procedure: 19 g of sodium styrenesulfonate (SSNa) (available from Sigma-Aldrich Corp.) and 1 g of 2-Allylhexafluoro-isopropanol are fully dissolved in 0.24 L of dimethylsulfoxide (DMSO) with heating. Then, 0.1 g of azobisisobutyronitrile (AIBN) is added dropwise to the DMSO solution. The monomers are polymerized for 24 hours or more. The polymerization is carried out varying the content of the allylhexafluoro-isopropanol (2, 5, 10, and 20 wt %). with heating The monomers are polymerized for 24 hours or more

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

Procedure: Preparation of 1,1,1-trifluoro-2-trifluoromethyl-2,5-pentanediol and 1,1,1-trifluoro-2 -trifluoromethyl-2,4-pentanediol: To a 3-necked, 3-L round bottomed flask equipped with an overhead stirrer, digital thermometer and a 1-L constant-pressure addition funnel with a nitrogen inlet was added 974 mL (1.95 mol) of borane-dimethylsulfide complex (2.0 M in tetrahydrofuran). The addition funnel was charged with a solution of 353 g (1.7 mol) of 1,1,1-trifluoro-2-trifluoromethyl-4-penten-2-ol in 400 mL of anhydrous tetrahydrofuran. The flask was cooled and the olefin was added slowly with stirring while maintaining a temperature below 15° C. The mixture was stirred at room temperature for two days after which time it was recooled and 750 mL (2.25 mol) of 3M NaOH was added carefully. The reaction mixture was reduced in volume on a rotary evaporator and subsequently co-evaporated with two 500 mL portions of diethyl ether. The resulting heavy oil was taken up in 300 mL of THF and the solution transferred to a 1-L 3-necked round-bottomed flask equipped with a 250-mL addition funnel, a digital thermometer and a magnetic stir bar. The addition funnel was charged with 250 mL of 30% hydrogen peroxide. The flask was cooled and the hydrogen peroxide added slowly with stirring. After stirring overnight at room temperature, the solution was diluted with 1 L of diethyl ether and adjusted to pH 6 (wet litmus) with 5% HCl. The ether layer was separated and the aqueous layer was extracted with 2×500 mL of ether. The combined organic phases were washed with 2×500 mL of saturated ammonium chloride and brine, dried over MgSO4 and evaporated to a crude yield of 379 g of a 45:55 (2°:1°) mixture of the two diols. The diols were separated by distillation through a 12″ Vigreux, bp 47° C. at 1.0 mm Hg (2° alcohol) and bp 55° C. at 1.0 mm Hg (1° alcohol). The 1° alcohol is a viscous oil while the 2° alcohol is a low melting solid. The flask was cooled while maintaining a temperature below 15° C The mixture was stirred at room temperature for two days after which time it The reaction mixture was reduced in volume on a rotary evaporator and subsequently co-evaporated with two 500 mL portions of diethyl ether the solution transferred to a 1-L 3-necked round-bottomed flask equipped with a 250-mL addition funnel The addition funnel was charged with 250 mL of 30% hydrogen peroxide The flask was cooled the hydrogen peroxide added slowly with stirring After stirring overnight at room temperature the solution was diluted with 1 L of diethyl ether The ether layer was separated the aqueous layer was extracted with 2×500 mL of ether The combined organic phases were washed with 2×500 mL of saturated ammonium chloride and brine dried over MgSO4 evaporated to a crude yield of 379 g of a 45:55 (2°:1°) mixture of the two diols The diols were separated by distillation through a 12″ Vigreux, bp 47° C. at 1.0 mm Hg (2° alcohol) and bp 55° C. at 1.0 mm Hg (1° alcohol) The 1° alcohol while the 2° alcohol

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

Procedure: Preparation of 1,1,1-trifluoro-2-trifluoromethyl-2,5-pentanediol and 1,1,1-trifluoro-2 -trifluoromethyl-2,4-pentanediol: To a 3-necked, 3-L round bottomed flask equipped with an overhead stirrer, digital thermometer and a 1-L constant-pressure addition funnel with a nitrogen inlet was added 974 mL (1.95 mol) of borane-dimethylsulfide complex (2.0 M in tetrahydrofuran). The addition funnel was charged with a solution of 353 g (1.7 mol) of 1,1,1-trifluoro-2-trifluoromethyl-4-penten-2-ol in 400 mL of anhydrous tetrahydrofuran. The flask was cooled and the olefin was added slowly with stirring while maintaining a temperature below 15° C. The mixture was stirred at room temperature for two days after which time it was recooled and 750 mL (2.25 mol) of 3M NaOH was added carefully. The reaction mixture was reduced in volume on a rotary evaporator and subsequently co-evaporated with two 500 mL portions of diethyl ether. The resulting heavy oil was taken up in 300 mL of THF and the solution transferred to a 1-L 3-necked round-bottomed flask equipped with a 250-mL addition funnel, a digital thermometer and a magnetic stir bar. The addition funnel was charged with 250 mL of 30% hydrogen peroxide. The flask was cooled and the hydrogen peroxide added slowly with stirring. After stirring overnight at room temperature, the solution was diluted with 1 L of diethyl ether and adjusted to pH 6 (wet litmus) with 5% HCl. The ether layer was separated and the aqueous layer was extracted with 2×500 mL of ether. The combined organic phases were washed with 2×500 mL of saturated ammonium chloride and brine, dried over MgSO4 and evaporated to a crude yield of 379 g of a 45:55 (2°:1°) mixture of the two diols. The diols were separated by distillation through a 12″ Vigreux, bp 47° C. at 1.0 mm Hg (2° alcohol) and bp 55° C. at 1.0 mm Hg (1° alcohol). The 1° alcohol is a viscous oil while the 2° alcohol is a low melting solid. The flask was cooled while maintaining a temperature below 15° C The mixture was stirred at room temperature for two days after which time it The reaction mixture was reduced in volume on a rotary evaporator and subsequently co-evaporated with two 500 mL portions of diethyl ether the solution transferred to a 1-L 3-necked round-bottomed flask equipped with a 250-mL addition funnel The addition funnel was charged with 250 mL of 30% hydrogen peroxide The flask was cooled the hydrogen peroxide added slowly with stirring After stirring overnight at room temperature the solution was diluted with 1 L of diethyl ether The ether layer was separated the aqueous layer was extracted with 2×500 mL of ether The combined organic phases were washed with 2×500 mL of saturated ammonium chloride and brine dried over MgSO4 evaporated to a crude yield of 379 g of a 45:55 (2°:1°) mixture of the two diols The diols were separated by distillation through a 12″ Vigreux, bp 47° C. at 1.0 mm Hg (2° alcohol) and bp 55° C. at 1.0 mm Hg (1° alcohol) The 1° alcohol while the 2° alcohol