1-fluoro-4-(4-fluorophenyl)sulfinylbenzene

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 100 mL four-necked flask, 360 g (3.75 moles) of methanesulfonate and 35.5 g (0.25 mole) of phosphorus pentoxide were fed, and the atmosphere was replaced with nitrogen, followed by heating the mixture at 100° C. to dissolve it. After cooling thereof, 59.6 g (0.25 mole) of bis(4-fluorophenyl)sulfoxide and 87.5 g (0.25 mole) of 9,9-bis(4-hydroxyphenyl)-9H-fluorene were fed to the solution, and the resulting mixture was allowed to react by stirring at 50° C. for 2 hours. Subsequently, 2000 mL of ice water and 1000 mL of methanol were mixed with each other and the above reaction solution was added to this mixture. To this, 1000 mL of methylene chloride, 500 mL of water and 40.6 g (0.26 mole) of lithium trifluoromethanesulfonate were added, and the resulting mixture was stirred for 2 hours. The methylene chloride layer was washed 3 times with 500 mL of water and concentrated under reduced pressure to obtain white solids, which was then subjected to a silica gel chromatography. Fractions containing the desired products were collected and concentrated under reduced pressure to obtain 54.1 g of trifluoromethanesulfonate [9,9-bis(4-hydroxyphenyl)-9H-fluorene-2-yl]bis(4-fluorophenyl)sulfonium. The yield was 30%. In a 50 mL four-necked flask, 5.41 g of this crude product was allowed to dissolve into 10.8 g of dimethylformamide, and 0.84 g (0.021 mole) of sodium hydroxide and 0.061 g (1.5×10−4 mole) of tetrabutylammonium hydrosulfate were added to the resulting solution, followed by addition of 2.09 g (0.019 mole) of benzene thiol thereto dropwise and stirring of the resulting mixture for 3 hours. To this mixture, 55 mL of methylene chloride was fed, and the resulting mixture was washed 3 times with 50 mL of water, followed by concentrating the resultant under reduced pressure to obtain 6.89 g of a crude product. To a 50 mL four-necked flask, this crude product and 50.0 g of dichloroethane were fed, and the crude product was allowed to dissolve into dichloroethane, followed by addition of 20.0 g of ethanol and 0.125 g (3.8×10−4 mole) of sodium tungstate dihydrate to the resulting solution and stirring thereof. To this, 6.80 g (0.060 mole) of 30% aqueous hydrogen peroxide solution was added dropwise, and the resulting mixture was heated to 50° C. and stirred for 3 hours. To the resultant, 50 mL of dichloroethane was fed, and the resulting mixture was washed 3 times with 50 mL of water, followed by concentrating the mixture under reduced pressure to obtain 6.37 g of a crude product. To a 50 mL four-necked flask, this crude product and 40 mL of dimethylformamide were fed, and the crude product was allowed to dissolve into dimethylformamide, followed by addition of 4.20 g (0.030 mole) of potassium carbonate to the resulting solution. To the resulting mixture, 2.06 g (0.015 mole) of methyl iodide was added dropwise, and the mixture was stirred for 3 hours. To this mixture, 40 mL of methylene chloride was fed, and the resulting mixture was washed 3 times with 40 mL of water, followed by concentrating the resultant under reduced pressure to obtain a crude product. The MALDI-TOFMASS of the crude product was measured to find a peak at 1308.32, so that coexistence of single fluorene bisphenol molecules wherein sulfoniation occurred at 2 positions (compound No. 5B) was confirmed. The crude product was subjected to a silica gel chromatography and fractions containing the desired product were collected, followed by concentrating thereof under reduced pressure to obtain the compound No. 5. The yielded amount was 3.41 g and the yield was 46%. to dissolve it After cooling to react was added to this mixture the resulting mixture was stirred for 2 hours The methylene chloride layer was washed 3 times with 500 mL of water concentrated under reduced pressure to obtain white solids, which were collected concentrated under reduced pressure