1,1-dibromo-1,2,2,2-tetrafluoroethane

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4-(Trifluoromethoxy)cyclopropoxybenzene (3 g) was dissolved in tetrahydrofuran (100 ml) and the solution was cooled to −78° C. under a nitrogen atmosphere. tert-Butyllithium (22.9 ml, 1.5M in pentane) was added dropwise and the solution was stirred for 3 hours. Dibromotetrafluoroethane (8.2 ml) was added dropwise and the reaction mixture was stirred at −78° C. for 2 hours. The reaction was quenched by the dropwise addition of water (50 ml). The product was extracted with diethyl ether. The combined organic fractions were dried (brine, MgSO4) and concentrated in vacuo. The residue was purified on silica using hexane as eluant, to yield the product as a colourless oil (2.2 g). 1H NMR (360 MHz, CDCl3) δ 0.86 (4H, m), 3.79 (1H, m), 7.15 (1H, dd, J 8.9, 2.7 Hz), 7.24 (1H, d, J 8.9 Hz), 7.42 (1H, d, J 2.7 Hz). the reaction mixture was stirred at −78° C. for 2 hours The reaction was quenched by the dropwise addition of water (50 ml) The product was extracted with diethyl ether The combined organic fractions were dried (brine, MgSO4) concentrated in vacuo The residue was purified on silica

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

Procedure: Into a solution of TMPMgCl LiCl (1.0 M×6.8 mL, 6.8 mmol) in THF (5.0 mL) at −45° C. was added dropwise a solution of tert-butyl 5-bromo-2,4-difluoronicotinate (1.32 g, 4.5 mmol) in THF (5.0 mL). The mixture was stirred for 15 min then dibromotetrafluoroethane (1.0 mL, 6.8 mmol) was added. After 15 min at −45° C., the temperature was allowed to rise to room temperature. The reaction was quenched with saturated NH4Cl and extracted with ethyl acetate. The organic layers were combined, dried over sodium sulfate and evaporated. The residue was purified by silica chromatography (0-10% ethyl acetate in hexanes) to give tert-butyl 5,6-dibromo-2,4-difluoronicotinate (1.29 g, 77%). After 15 min at −45° C. to rise to room temperature The reaction was quenched with saturated NH4Cl extracted with ethyl acetate dried over sodium sulfate evaporated The residue was purified by silica chromatography (0-10% ethyl acetate in hexanes)

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A dry 500-mL three-neck flask was flushed with N2 and was charged with 8-(2-ethylhexoxy)-4-(2-ethylhexyl)thieno[2,3-f]benzothiophene (8.4 g, 0.020 mol) and THF (200 mL, 0.1 M) via deoxygenated syringe. The reaction flask was cooled to −78° C. and a 2.0 M solution of n-butyllithium in hexanes (10 mL, 0.020 mol) was added dropwise via deoxygenated syringe. After 30 minutes of stirring at −78° C., dibromotetrafluoroethane (7.8 g, 0.030 mol) was added to the reaction flask and stirring continued for 1 hour at −78° C. The cooling bath was removed and the reaction mixture was allowed to warm up to ambient temperature. As the reaction was completed, cool DI water (50 mL) was slowly added to the reaction flask. Then, the reaction mixture was poured into 150 mL of cool water and extracted with hexanes (200 mL) three times. The combined organic layer was dried over anhydrous magnesium sulfate (MgSO4). After the product was filtered, the solvent was removed by rotary evaporation. The product was purified using column chromatography on silica gel with hexanes/chloroform (gradient) to yield colorless oil (4.2 g, 42%). A dry 500-mL three-neck flask was flushed with N2 via deoxygenated syringe via deoxygenated syringe stirring continued for 1 hour at −78° C The cooling bath was removed to warm up to ambient temperature cool DI water (50 mL) was slowly added to the reaction flask Then, the reaction mixture was poured into 150 mL of cool water extracted with hexanes (200 mL) three times The combined organic layer was dried over anhydrous magnesium sulfate (MgSO4) After the product was filtered the solvent was removed by rotary evaporation The product was purified

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4-(Trifluoromethoxy)cyclopropoxybenzene (3 g) was dissolved in tetrahydrofuran (100 ml) and the solution was cooled to −78° C. under a nitrogen atmosphere. tert-Butyllithium (22.9 ml, 1.5M in pentane) was added dropwise and the solution was stirred for 3 hours. Dibromotetrafluoroethane (8.2 ml) was added dropwise and the reaction mixture was stirred at −78° C. for 2 hours. The reaction was quenched by the dropwise addition of water (50 ml). The product was extracted with diethyl ether. The combined organic fractions were dried (brine, MgSO4) and concentrated in vacuo. The residue was purified on silica using hexane as eluant, to yield the product as a colourless oil (2.2 g). 1H NMR (360 MHz, CDCl3) δ 0.86 (4H, m), 3.79 (1H, m), 7.15 (1H, dd, J 8.9, 2.7 Hz), 7.24 (1H, d, J 8.9 Hz), 7.42 (1H, d, J 2.7 Hz). the reaction mixture was stirred at −78° C. for 2 hours The reaction was quenched by the dropwise addition of water (50 ml) The product was extracted with diethyl ether The combined organic fractions were dried (brine, MgSO4) concentrated in vacuo The residue was purified on silica