1-(benzenesulfonyl)-4-fluorobenzene

Conditions: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixture of 1-fluoro-4-iodobenzene (448 mg, 2.00 mmol) and sodium benzenesulfinate (755 mg, 1.50 mmol) in DMF (5 mL) under a nitrogen atmosphere was added copper (I) trifluoromethanesulfonate benzene complex (443 mg, 2.70 mmol). The reaction was stirred at 65° C. overnight, diluted with ethyl acetate then washed with water and brine. The organic layer was dried over sodium sulfate and concentrated in vacuo to give the crude material which was purified by flash column chromatography (85:15 to 80:20 hexanes/ethyl acetate) to give 1-fluoro-4-(phenylsulfonyl)-benzene (103 mg, 22%) as a white solid: 1H NMR (CDCl3, 300 MHz) δ 7.99-7.92 (m, 4H), 7.58-7.49 (m, 3H), 7.18 (t, J=8.4 Hz, 1H), 7.21-7.15 (m, 1H). was added copper (I) trifluoromethanesulfonate benzene complex (443 mg, 2.70 mmol) then washed with water and brine The organic layer was dried over sodium sulfate concentrated in vacuo to give the crude material which was purified by flash column chromatography (85:15 to 80:20 hexanes/ethyl acetate)

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 6.60 g (0.0330 mole) of N,N-dimethyl-4-hydroxybenzenesulfonamide dissolved in 150 ml of DMSO was added 1.32 g (0.0330 mole) of NaOH. The mixture was heated at 60° C. for 10 minutes and 7.1 g (0.030 mole) of 4-fluorophenyl phenyl sulfone was added. The reaction mixture was heated at 100° C. for 3 hrs and at 125° C. for 3 hrs and cooled. The mixture was poured into a solution of 200 ml of 20% aqueous NaOH and 500 ml of water. The crystalline product was collected, washed well with water and dried, which gave 11.5 g (92% yield) of product. Recrystallization from aqueous DMSO followed by recrystallization from ethanol afforded purified N,N-dimethyl-4-(4-(phenylsulfonyl)phenoxy)benzenesulfonamide, mp 99°-100° C. The reaction mixture was heated at 100° C. for 3 hrs and at 125° C. for 3 hrs cooled The crystalline product was collected washed well with water dried

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 9.0 g (0.0550 mole) of 3,4-dichlorophenol dissolved in 150 ml of DMSO was added 2.20 g (0.0550 mole) of NaOH. The mixture was heated to 60° C. and 12.5 g (0.0529 mole) of 4-fluorophenyl phenyl sulfone was added. The reaction mixture was heated at 125° C. for 3.25 hrs and cooled. The mixture was poured into a solution of 100 ml of 20% aqueous NaOH and 600 ml of water. The crystalline product was collected by filtration, washed well with water and partially dried. Recrystallization from ethanol afforded 16.9 g (84.5% yield) of purified 4-(4-(phenylsulfonyl)phenoxy)-1,2-dichlorobenzene, mp 145°-146° C. The reaction mixture was heated at 125° C. for 3.25 hrs cooled The crystalline product was collected by filtration washed well with water partially dried Recrystallization from ethanol

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 6.60 g (0.0330 mole) of N,N-dimethyl-4-hydroxybenzenesulfonamide dissolved in 150 ml of DMSO was added 1.32 g (0.0330 mole) of NaOH. The mixture was heated at 60° C. for 10 minutes and 7.1 g (0.030 mole) of 4-fluorophenyl phenyl sulfone was added. The reaction mixture was heated at 100° C. for 3 hrs and at 125° C. for 3 hrs and cooled. The mixture was poured into a solution of 200 ml of 20% aqueous NaOH and 500 ml of water. The crystalline product was collected, washed well with water and dried, which gave 11.5 g (92% yield) of product. Recrystallization from aqueous DMSO followed by recrystallization from ethanol afforded purified N,N-dimethyl-4-(4-(phenylsulfonyl)phenoxy)benzenesulfonamide, mp 99°-100° C. The reaction mixture was heated at 100° C. for 3 hrs and at 125° C. for 3 hrs cooled The crystalline product was collected washed well with water dried

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 9.0 g (0.0550 mole) of 3,4-dichlorophenol dissolved in 150 ml of DMSO was added 2.20 g (0.0550 mole) of NaOH. The mixture was heated to 60° C. and 12.5 g (0.0529 mole) of 4-fluorophenyl phenyl sulfone was added. The reaction mixture was heated at 125° C. for 3.25 hrs and cooled. The mixture was poured into a solution of 100 ml of 20% aqueous NaOH and 600 ml of water. The crystalline product was collected by filtration, washed well with water and partially dried. Recrystallization from ethanol afforded 16.9 g (84.5% yield) of purified 4-(4-(phenylsulfonyl)phenoxy)-1,2-dichlorobenzene, mp 145°-146° C. The reaction mixture was heated at 125° C. for 3.25 hrs cooled The crystalline product was collected by filtration washed well with water partially dried Recrystallization from ethanol