1-fluoro-4-prop-2-enoxybenzene

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: 381.8 parts of oily 4-allyloxy-fluorobenzene are heated in an oil-bath for 8 hours at a temperature of about 245° -250° C. After cooling, the reaction mixture is poured onto 1200 parts of hexane. The mixture is extracted three times with sodium hydroxide solution 20% (total volume of sodium hydroxide: 2000 parts). The aqueous layer is washed with petroleum ether, acidified with 1300 parts of concentrated hydrochloric acid solution and extracted with ether. The extract is dried over calcium chloride, filtered and evaporated. The oily residue is distilled in vacuo, yielding 313.6 parts of 2-allyl-4-fluorophenol; bp 143° C at 48 mm. pressure; nD20 : 1.5225; d2020 : 1.1130. After cooling The mixture is extracted three times with sodium hydroxide solution 20% (total volume of sodium hydroxide: 2000 parts) The aqueous layer is washed with petroleum ether extracted with ether The extract is dried over calcium chloride filtered evaporated The oily residue is distilled in vacuo

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

Procedure: A mixture of 336.3 parts of 4-fluorophenol, 417.5 parts of allyl bromide, 420 parts of potassium carbonate and 480 parts of acetone is stirred and refluxed for 8 hours. After cooling to room temperature, 2250 parts of water are added. The aqueous layer is separated and extracted twice with ether. The combined extracts are washed successively twice with sodium hydroxide solution 10% and twice with sodium chloride solution, dried over potassium carbonate, filtered and evaporated. The oily residue is distilled in vacuo, yielding 381.8 parts of 4-allyloxy-fluorobenzene; bp. 93° C at 23 mm. pressure; nD20 : 1.4950; d2020 : 1.070. refluxed for 8 hours The aqueous layer is separated extracted twice with ether The combined extracts are washed successively twice with sodium hydroxide solution 10% and twice with sodium chloride solution dried over potassium carbonate filtered evaporated The oily residue is distilled in vacuo

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

Procedure: To a solution of 4-fluorophenol (1p) (30 g, 268.0 mmol) in acetone (250 mL), anhydrous K2CO3 (65 g, 468.3 mmol) was added followed by 3-bromo-propene (2p) (28 mL, 321.1 mmol). The resulting mixture was refluxed for 16 hours, cooled to room temperature and then poured onto ice water (500 mL). The aqueous layer was extracted with ether (3×250 mL) and the combined organic layers were washed with 2 M NaOH (2×150 mL) and dried over a mixture of anhydrous K2CO3 and Na2SO4. The solvent was removed under vacuum to afford the desired product (3p) (40.4 g, 99%) as light yellow oil. 1H NMR (400 MHz, CDCl3) δ7.01-6.92 (m, 2H), 6.89-6.82 (m, 2H), 6.10-6.82 (m, 1H), 5.44-5.41 (m, 1H), 5.39-5.37 (m, 1H), 4.51-4.448 (m, 2H). The resulting mixture was refluxed for 16 hours poured onto ice water (500 mL) The aqueous layer was extracted with ether (3×250 mL) the combined organic layers were washed with 2 M NaOH (2×150 mL) dried over a mixture of anhydrous K2CO3 and Na2SO4 The solvent was removed under vacuum

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

Procedure: To a solution of 4-fluorophenol (1p) (30 g, 268.0 mmol) in acetone (250 mL), anhydrous K2CO3 (65 g, 468.3 mmol) was added followed by 3-bromo-propene (2p) (28 mL, 321.1 mmol). The resulting mixture was refluxed for 16 hours, cooled to room temperature and then poured onto ice water (500 mL). The aqueous layer was extracted with ether (3×250 mL) and the combined organic layers were washed with 2 M NaOH (2×150 mL) and dried over a mixture of anhydrous K2CO3 and Na2SO4. The solvent was removed under vacuum to afford the desired product (3p) (40.4 g, 99%) as light yellow oil. 1H NMR (400 MHz, CDCl3) δ7.01-6.92 (m, 2H), 6.89-6.82 (m, 2H), 6.10-6.82 (m, 1H), 5.44-5.41 (m, 1H), 5.39-5.37 (m, 1H), 4.51-4.448 (m, 2H). The resulting mixture was refluxed for 16 hours poured onto ice water (500 mL) The aqueous layer was extracted with ether (3×250 mL) the combined organic layers were washed with 2 M NaOH (2×150 mL) dried over a mixture of anhydrous K2CO3 and Na2SO4 The solvent was removed under vacuum

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

Procedure: This compound was prepared from 4-fluorophenol and allyl bromide according to the process described in Example 5, stage A. The solvent used is acetone and the reaction was carried out in the presence of sodium hydroxide.

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

Procedure: To a solution of 4-fluorophenol (22.4 g, 200 mmol) in DCM (200 mL) was added 50% NaOH (aq) (100 mL), 3-bromoprop-1-ene (26.0 mL, 300.0 mmol) and tetra-n-butylammonium bromide (1.90 g, 6.0 mmol). The suspension was stirred at room temperature for 24 h. The layers were separated and washed with water (2×100 mL), brine (100 mL) and dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified by chromatography (0-20% EtOAc in hexanes) to provide the desired 1-(allyloxy)-4-fluorobenzene (852) (29.7 g, 97.8%) as a colorless oil. The layers were separated washed with water (2×100 mL), brine (100 mL) dried over sodium sulfate filtered concentrated in vacuo The residue was purified by chromatography (0-20% EtOAc in hexanes)

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

Procedure: To a solution of 4-fluorophenol (22.4 g, 200 mmol) in DCM (200 mL) was added 50% NaOH (aq) (100 mL), 3-bromoprop-1-ene (26.0 mL, 300.0 mmol) and tetra-n-butylammonium bromide (1.90 g, 6.0 mmol). The suspension was stirred at room temperature for 24 h. The layers were separated and washed with water (2×100 mL), brine (100 mL) and dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified by chromatography (0-20% EtOAc in hexanes) to provide the desired 1-(allyloxy)-4-fluorobenzene (852) (29.7 g, 97.8%) as a colorless oil. The layers were separated washed with water (2×100 mL), brine (100 mL) dried over sodium sulfate filtered concentrated in vacuo The residue was purified by chromatography (0-20% EtOAc in hexanes)

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

Procedure: 381.8 parts of oily 4-allyloxy-fluorobenzene are heated in an oil-bath for 8 hours at a temperature of about 245° -250° C. After cooling, the reaction mixture is poured onto 1200 parts of hexane. The mixture is extracted three times with sodium hydroxide solution 20% (total volume of sodium hydroxide: 2000 parts). The aqueous layer is washed with petroleum ether, acidified with 1300 parts of concentrated hydrochloric acid solution and extracted with ether. The extract is dried over calcium chloride, filtered and evaporated. The oily residue is distilled in vacuo, yielding 313.6 parts of 2-allyl-4-fluorophenol; bp 143° C at 48 mm. pressure; nD20 : 1.5225; d2020 : 1.1130. After cooling The mixture is extracted three times with sodium hydroxide solution 20% (total volume of sodium hydroxide: 2000 parts) The aqueous layer is washed with petroleum ether extracted with ether The extract is dried over calcium chloride filtered evaporated The oily residue is distilled in vacuo

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

Procedure: A mixture of 336.3 parts of 4-fluorophenol, 417.5 parts of allyl bromide, 420 parts of potassium carbonate and 480 parts of acetone is stirred and refluxed for 8 hours. After cooling to room temperature, 2250 parts of water are added. The aqueous layer is separated and extracted twice with ether. The combined extracts are washed successively twice with sodium hydroxide solution 10% and twice with sodium chloride solution, dried over potassium carbonate, filtered and evaporated. The oily residue is distilled in vacuo, yielding 381.8 parts of 4-allyloxy-fluorobenzene; bp. 93° C at 23 mm. pressure; nD20 : 1.4950; d2020 : 1.070. refluxed for 8 hours The aqueous layer is separated extracted twice with ether The combined extracts are washed successively twice with sodium hydroxide solution 10% and twice with sodium chloride solution dried over potassium carbonate filtered evaporated The oily residue is distilled in vacuo