4-chloro-1-ethenyl-2-fluorobenzene

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

Procedure: To a mechanically stirred mixture of impure 4-chloro-2-fluoro-1-vinylbenzene (26.76 g, 154 mmol), sodium p-toluenesulfinate (28.8 g, 161 mmol) and NaI (34.6 g, 231 mmol) in MeCN (700 mL) was added (NH4)2Ce(NO3)6 (169 g, 308 mmol) portionwise. The mixture was stirred under a nitrogen atmosphere during 3 h at room temperature. The liquid was separated by decantation and the solids were washed with MeCN (3×100 mL). The solvent was evaporated in vacuo and re-dissolved in EtOAc (500 mL). The organic layer was washed with brine (400 mL), aqueous 10 wt % Na2S2O3 (2×200 mL) and brine (200 mL). The organic layer was dried (Na2SO4) and the solvent was evaporated to arrive at 51.86 g of crude title compound as a yellow solid. The liquid was separated by decantation the solids were washed with MeCN (3×100 mL) The solvent was evaporated in vacuo re-dissolved in EtOAc (500 mL) The organic layer was washed with brine (400 mL), aqueous 10 wt % Na2S2O3 (2×200 mL) and brine (200 mL) The organic layer was dried (Na2SO4) the solvent was evaporated

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

Procedure: To a mechanically stirred mixture of impure 4-chloro-2-fluoro-1-vinylbenzene (26.76 g, 154 mmol), sodium p-toluenesulfinate (28.8 g, 161 mmol) and NaI (34.6 g, 231 mmol) in MeCN (700 mL) was added (NH4)2Ce(NO3)6 (169 g, 308 mmol) portionwise. The mixture was stirred under a nitrogen atmosphere during 3 h at room temperature. The liquid was separated by decantation and the solids were washed with MeCN (3×100 mL). The solvent was evaporated in vacuo and re-dissolved in EtOAc (500 mL). The organic layer was washed with brine (400 mL), aqueous 10 wt % Na2S2O3 (2×200 mL) and brine (200 mL). The organic layer was dried (Na2SO4) and the solvent was evaporated to arrive at 51.86 g of crude title compound as a yellow solid. The liquid was separated by decantation the solids were washed with MeCN (3×100 mL) The solvent was evaporated in vacuo re-dissolved in EtOAc (500 mL) The organic layer was washed with brine (400 mL), aqueous 10 wt % Na2S2O3 (2×200 mL) and brine (200 mL) The organic layer was dried (Na2SO4) the solvent was evaporated

Conditions: temp:15.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of KOt-Bu (19.5 g, 174 mmol) in dry THF (300 mL) was cooled with an ice/water bath. Portionwise addition of MePPh3Br (62.2 g, 174 mmol) resulted in a suspension, which was stirred for 5 min at 0° C. and for 1 h at 15° C. Subsequently, the temperature was lowered to 0° C. and a solution of 4-chloro-2-fluorobenzaldehyde (25.1 g, 158 mmol) in dry THF (100 mL) was added dropwise. The temperature was raised to room temperature slowly. The reaction mixture was stirred at room temperature for 20 h. Addition of brine (100 mL) resulted in a clear two phase system and a white solid. The combination of layers was decanted from the solid. The layers were separated, the aqueous layer was combined with the solid residue and Et2O (200 mL). The combination of layers was decanted from the solid. The layers were separated, the combination of organic layers was dried (Na2SO4) and concentrated at a controlled vacuum of 100 mbar. The residual oil was combined with pentane (300 mL) and Na2SO4. The suspension was triturated. Filtration and pentane washing provided a filtrate, which was concentrated at a controlled vacuum of 100 mbar to arrive at 26.76 g (97%, 90% purity) of impure title compound as a yellow oil. Portionwise addition of MePPh3Br (62.2 g, 174 mmol) resulted in a suspension, which was lowered to 0° C. The temperature was raised to room temperature slowly The reaction mixture was stirred at room temperature for 20 h resulted in a clear two phase system The combination of layers was decanted from the solid The layers were separated The combination of layers was decanted from the solid The layers were separated the combination of organic layers was dried (Na2SO4) concentrated at a controlled vacuum of 100 mbar The suspension was triturated Filtration and pentane washing provided a filtrate, which was concentrated at a controlled vacuum of 100 mbar

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

Procedure: To a mechanically stirred mixture of impure 4-chloro-2-fluoro-1-vinylbenzene (26.76 g, 154 mmol), sodium p-toluenesulfinate (28.8 g, 161 mmol) and NaI (34.6 g, 231 mmol) in MeCN (700 mL) was added (NH4)2Ce(NO3)6 (169 g, 308 mmol) portionwise. The mixture was stirred under a nitrogen atmosphere during 3 h at room temperature. The liquid was separated by decantation and the solids were washed with MeCN (3×100 mL). The solvent was evaporated in vacuo and re-dissolved in EtOAc (500 mL). The organic layer was washed with brine (400 mL), aqueous 10 wt % Na2S2O3 (2×200 mL) and brine (200 mL). The organic layer was dried (Na2SO4) and the solvent was evaporated to arrive at 51.86 g of crude title compound as a yellow solid. The liquid was separated by decantation the solids were washed with MeCN (3×100 mL) The solvent was evaporated in vacuo re-dissolved in EtOAc (500 mL) The organic layer was washed with brine (400 mL), aqueous 10 wt % Na2S2O3 (2×200 mL) and brine (200 mL) The organic layer was dried (Na2SO4) the solvent was evaporated

Conditions: temp:15.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of KOt-Bu (19.5 g, 174 mmol) in dry THF (300 mL) was cooled with an ice/water bath. Portionwise addition of MePPh3Br (62.2 g, 174 mmol) resulted in a suspension, which was stirred for 5 min at 0° C. and for 1 h at 15° C. Subsequently, the temperature was lowered to 0° C. and a solution of 4-chloro-2-fluorobenzaldehyde (25.1 g, 158 mmol) in dry THF (100 mL) was added dropwise. The temperature was raised to room temperature slowly. The reaction mixture was stirred at room temperature for 20 h. Addition of brine (100 mL) resulted in a clear two phase system and a white solid. The combination of layers was decanted from the solid. The layers were separated, the aqueous layer was combined with the solid residue and Et2O (200 mL). The combination of layers was decanted from the solid. The layers were separated, the combination of organic layers was dried (Na2SO4) and concentrated at a controlled vacuum of 100 mbar. The residual oil was combined with pentane (300 mL) and Na2SO4. The suspension was triturated. Filtration and pentane washing provided a filtrate, which was concentrated at a controlled vacuum of 100 mbar to arrive at 26.76 g (97%, 90% purity) of impure title compound as a yellow oil. Portionwise addition of MePPh3Br (62.2 g, 174 mmol) resulted in a suspension, which was lowered to 0° C. The temperature was raised to room temperature slowly The reaction mixture was stirred at room temperature for 20 h resulted in a clear two phase system The combination of layers was decanted from the solid The layers were separated The combination of layers was decanted from the solid The layers were separated the combination of organic layers was dried (Na2SO4) concentrated at a controlled vacuum of 100 mbar The suspension was triturated Filtration and pentane washing provided a filtrate, which was concentrated at a controlled vacuum of 100 mbar