1-chloro-4-[(2-methylpropan-2-yl)oxy]benzene

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

Procedure: A solution of 20.2 g (0.10 mol) of diphenyl sulfoxide in 200 g of methylene chloride was cooled on an ice bath. To the solution, 5.3 g (0.052 mol) of triethylamine was added and 32.6 g (0.30 mol) of trimethylsilyl chloride was dropwised at 0° to 20° C. Stirring was continued at 0° to 10° C. for 15 minutes. To this solution, a Grignard reagent which was conventionally prepared from 55.4 g (0.30 mol) of 4-tert-butoxychlorobenzene, 7.3 g (0.30 mol) of magnesium, and 90 g of THF was dropwised at 0° to 10 ° C. Stirring was continued at 0° to 10° C. for 30 minutes. 500 g of 20% ammonium chloride aqueous solution was added to the reaction mixture. To the organic layer was added 1,000 g of chloroform. The organic layer was once washed with 200 g of water and the solvent was evaporated. The residue was purified by recrystalization, isolating 26.6 g (yield 72%) of (4-tert-butoxyphenyl)diphenylsulfonium chloride with 98% purity. was dropwised at 0° to 20° C was dropwised at 0° to 10 ° C Stirring was continued at 0° to 10° C. for 30 minutes The organic layer was once washed with 200 g of water the solvent was evaporated The residue was purified by recrystalization

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

Procedure: A solution of 17.8 g (0.052 mol) of bis(4-tertbutoxyphenyl) sulfoxide in 52 g of THF was cooled on an ice bath. To the solution, 5.3 g (0.052 mol) of triethylamine was added and 14.1 g (0.13 mol) of trimethylsilyl chloride was dropwised at 0° to 10° C. Stirring was continued at 0 to 10° C. for 30 minutes. To this solution, a Grignard reagent which was conventionally prepared from 24.0 g (0.13 mol) of 4-tert-butoxychlorobenzene, 3.2 g (0.13 mol) of magnesium, and 40 g of THF was dropwised at 0° to 10° C. Stirring was continued at 0° to 10° C. for 30 minutes. 300 g of 20% ammonium chloride aqueous solution was added to the reaction mixture. To the organic layer was added 500 g of chloroform. The organic layer was washed twice with 200 g of water and the solvent was evaporated and residue was purifie by column chromatography (silica gel, eluent: chloroform/methanol), isolating 9.3 g (yield 35%) of tris(4-tert-butoxyphenyl)sulfonium chloride with 99% purity. was dropwised at 0° to 10° C was dropwised at 0° to 10° C Stirring was continued at 0° to 10° C. for 30 minutes The organic layer was washed twice with 200 g of water the solvent was evaporated

Conditions: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a stirred solution of 60.0 g (0.164 mol) of bis-(4-t-butoxyphenyl) sulfoxide in 26.8 g (0.34 mol) of pyridine and 400 ml of tetrahydrofuran was dropped 126.57 g (0.34 mol) of trimethylsilyl nonafluorobutane sulfonate while keeping the temperature below −5° C. with a salted ice bath. After completion of the addition, the reaction temperature was raised to 5° C., followed by stirring for additional 20 minutes. A Grignard solution was prepared from 8.4 g (0.34 mol) of magnesium, 100 g of tetrahydrofuran and 68.6 g (0.38 mol) of 4-t-butoxy chlorobenzene, and added dropwise to the above solution at 0° C. The mixture was stirred for 2 hours at this temperature. Then water was added to decompose the excess Grignard reagent, and the inorganic salts were removed by filtration. The solution was concentrated to about 160 ml and extracted with a mixture of 1200 ml of dichloromethane, 600 g of a saturated aqueous solution of ammonium chloride and 600 ml water. The organic phase was washed twice with water and dried. The solvent was removed to yield an oily product which was then purified by column chromatography on silica gel using dichloromethane as the eluant. Thus, tris-(4-butoxyphenyl) sulfonium nonafluorobutane sulfonate was obtained as a slightly yellowish powder. The structure was confirmed by 1H-NMR (CDCl3) with δ=1.42 (s, 27H), 7.35-7.42 (d, 6H) and 7.78-7.93 ppm (d, 6H). the temperature below −5° C. After completion of the addition added dropwise to the above solution at 0° C The mixture was stirred for 2 hours at this temperature the inorganic salts were removed by filtration The solution was concentrated to about 160 ml extracted with a mixture of 1200 ml of dichloromethane, 600 g of a saturated aqueous solution of ammonium chloride and 600 ml water The organic phase was washed twice with water dried The solvent was removed to yield an oily product which was then purified by column chromatography on silica gel

Conditions: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a stirred solution of 60.0 g (0.164 mol) of bis-(4-t-butoxyphenyl) sulfoxide in 26.8 g (0.34 mol) of pyridine and 400 ml of tetrahydrofuran was dropped 126.57 g (0.34 mol) of trimethylsilyl nonafluorobutane sulfonate while keeping the temperature below −5° C. with a salted ice bath. After completion of the addition, the reaction temperature was raised to 5° C., followed by stirring for additional 20 minutes. A Grignard solution was prepared from 8.4 g (0.34 mol) of magnesium, 100 g of tetrahydrofuran and 68.6 g (0.38 mol) of 4-t-butoxy chlorobenzene, and added dropwise to the above solution at 0° C. The mixture was stirred for 2 hours at this temperature. Then water was added to decompose the excess Grignard reagent, and the inorganic salts were removed by filtration. The solution was concentrated to about 160 ml and extracted with a mixture of 1200 ml of dichloromethane, 600 g of a saturated aqueous solution of ammonium chloride and 600 ml water. The organic phase was washed twice with water and dried. The solvent was removed to yield an oily product which was then purified by column chromatography on silica gel using dichloromethane as the eluant. Thus, tris-(4-butoxyphenyl) sulfonium nonafluorobutane sulfonate was obtained as a slightly yellowish powder. The structure was confirmed by 1H-NMR (CDCl3) with δ=1.42 (s, 27H), 7.35-7.42 (d, 6H) and 7.78-7.93 ppm (d, 6H). the temperature below −5° C. After completion of the addition added dropwise to the above solution at 0° C The mixture was stirred for 2 hours at this temperature the inorganic salts were removed by filtration The solution was concentrated to about 160 ml extracted with a mixture of 1200 ml of dichloromethane, 600 g of a saturated aqueous solution of ammonium chloride and 600 ml water The organic phase was washed twice with water dried The solvent was removed to yield an oily product which was then purified by column chromatography on silica gel

Conditions: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a stirred solution of 60.0 g (0.164 mol) of bis-(4-t-butoxyphenyl) sulfoxide in 26.8 g (0.34 mol) of pyridine and 400 ml of tetrahydrofuran was dropped 75.6 g (0.34 mol) of trimethylsilyl 3,3,3,2,1,1-hexafluoropropane sulfonate while keeping the temperature below −5° C. with a salted ice bath. After completion of the addition, the reaction temperature was raised to 5° C., followed by stirring for 20 minutes. A Grignard solution was prepared from 8.4 g (0.34 mol) of magnesium, 100 g of tetrahydrofuran and 68.6 g (0.38 mol) of 4-t-butoxy chlorobenzene, and added dropwise to the above solution at 0° C. The mixture was stirred for 2 hours at this temperature. Then water was added to decompose the excess Grignard reagent, and the inorganic salts were removed by filtration. The solution was concentrated to about 160 ml and extracted with a mixture of 1200 ml of dichloromethane, 600 g of a saturated aqueous solution of ammonium chloride and 600 ml water. The organic phase was washed twice with water and dried. The solvent was removed to yield an oily product which was then purified by column chromatography on silica gel using dichloromethane as the eluant. Thus, tris-(4-butoxyphenyl) sulfonium 3,3,3,2,1,1-hexafluoropropane sulfonate was obtained as a slightly yellowish powder (m.p. 107° C.). The structure was confirmed by 1H-NMR (CDCl3) with δ=1.42 (s, 27H), 5.14-5.52 (d[m], 1H), 7.17-7.20 (d, 6H) and 7.55-7.60 ppm (d, 6H). the temperature below −5° C. After completion of the addition added dropwise to the above solution at 0° C The mixture was stirred for 2 hours at this temperature the inorganic salts were removed by filtration The solution was concentrated to about 160 ml extracted with a mixture of 1200 ml of dichloromethane, 600 g of a saturated aqueous solution of ammonium chloride and 600 ml water The organic phase was washed twice with water dried The solvent was removed to yield an oily product which was then purified by column chromatography on silica gel

Conditions: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a stirred solution of 60.0 g (0.164 mol) of bis-(4-t-butoxyphenyl) sulfoxide in 26.8 g (0.34 mol) of pyridine and 400 ml of tetrahydrofuran was dropped 75.6 g (0.34 mol) of trimethylsilyl 3,3,3,2,1,1-hexafluoropropane sulfonate while keeping the temperature below −5° C. with a salted ice bath. After completion of the addition, the reaction temperature was raised to 5° C., followed by stirring for 20 minutes. A Grignard solution was prepared from 8.4 g (0.34 mol) of magnesium, 100 g of tetrahydrofuran and 68.6 g (0.38 mol) of 4-t-butoxy chlorobenzene, and added dropwise to the above solution at 0° C. The mixture was stirred for 2 hours at this temperature. Then water was added to decompose the excess Grignard reagent, and the inorganic salts were removed by filtration. The solution was concentrated to about 160 ml and extracted with a mixture of 1200 ml of dichloromethane, 600 g of a saturated aqueous solution of ammonium chloride and 600 ml water. The organic phase was washed twice with water and dried. The solvent was removed to yield an oily product which was then purified by column chromatography on silica gel using dichloromethane as the eluant. Thus, tris-(4-butoxyphenyl) sulfonium 3,3,3,2,1,1-hexafluoropropane sulfonate was obtained as a slightly yellowish powder (m.p. 107° C.). The structure was confirmed by 1H-NMR (CDCl3) with δ=1.42 (s, 27H), 5.14-5.52 (d[m], 1H), 7.17-7.20 (d, 6H) and 7.55-7.60 ppm (d, 6H). the temperature below −5° C. After completion of the addition added dropwise to the above solution at 0° C The mixture was stirred for 2 hours at this temperature the inorganic salts were removed by filtration The solution was concentrated to about 160 ml extracted with a mixture of 1200 ml of dichloromethane, 600 g of a saturated aqueous solution of ammonium chloride and 600 ml water The organic phase was washed twice with water dried The solvent was removed to yield an oily product which was then purified by column chromatography on silica gel

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

Procedure: A Grignard reagent which was conventionally prepared using 24.3 g (1 mol) of magnesium, 203.2 g (1.1 mol) of 4-tert-butoxyphenyl chloride, and 280 g of THF was diluted with 500 g of THF and cooled to lower than -60° C. in a dry ice/methanol bath. Then 47.5 g (0.4 mol) of thionyl chloride diluted with 70 g of THF was added dropwise over 1 hour at less 0° C. After ripening for 1 hour in an ice bath, 36 g of water was added to decompose the excess of Grignard reagent. Separation was carried out by adding 1,000 g of methylene chloride and further 400 g of saturated ammonium chloride aqueous solution and 300 g of water. The organic layer was washed twice with 700 g of pure water. The organic layer was dried over magnesium sulfate and filtered and then evaporated. The resulting oily residue was recrystallized, isolating bis(4-tert-butoxyphenyl) sulfoxide in a yield of 60%. was added dropwise over 1 hour at less 0° C Separation by adding 1,000 g of methylene chloride and further 400 g of saturated ammonium chloride aqueous solution and 300 g of water The organic layer was washed twice with 700 g of pure water The organic layer was dried over magnesium sulfate filtered evaporated The resulting oily residue was recrystallized

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

Procedure: A Grignard reagent was conventionally prepared using 60.7 g (2.5 mol) of magnesium, 461 g (2.5 mol) of 4-tert-butoxyphenyl chloride, and 700 g of THF. The Grignard reagent solution was cooled in an ice water bath whereupon 59.5 g (0.5 mol) of thionyl chloride diluted with 100 g of THF was added dropwise at less 30° C. Reaction mixture was ripened for about 30 minutes. Thereafter, 277.8 g (1.25 mol) of trimethylsilyltrifluoromethane sulfonate was added dropwise at less 20° C. Reaction mixture was further ripened for 1 hour and thereafter, the reaction solution was allowed to stand overnight at room temperature. After the reaction solution was again cooled in an ice water bath, 1,800 g of 16.7% ammonium chloride aqueous solution (NH4Cl 300 g+H2O 1,500 g) was added thereto at a temperature not in excess of 30° C. After separation, 1,000 g of chloroform was added to the organic layer, which was washed three times using 1,000 g of water. Thereafter, the solvent was distilled off under reduced pressure by means of a rotary evaporator and the resulting oily residue was recrystallized, isolating tris(4-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate of 99% purity in an amount of 141 g (yield 45%). was added dropwise at less 30° C Reaction mixture Reaction mixture was further ripened for 1 hour to stand overnight at room temperature After the reaction solution was again cooled in an ice water bath excess of 30° C After separation, 1,000 g of chloroform was added to the organic layer, which was washed three times Thereafter, the solvent was distilled off under reduced pressure by means of a rotary evaporator the resulting oily residue was recrystallized

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

Procedure: A Grignard reagent was conventionally prepared using 60.7 g (2.5 mol) of magnesium, 461 g (2.5 mol) of 4-tert-butoxyphenyl chloride, and 700 g of THF. The Grignard reagent solution was cooled in an ice water bath whereupon 59.5 g (0.5 mol) of thionyl chloride diluted with 100 g of THF was added dropwise at less 30° C. Reaction mixture was ripened for about 30 minutes. Thereafter, 277.8 g (1.25 mol) of trimethylsilyltrifluoromethane sulfonate was added dropwise at less 20° C. Reaction mixture was further ripened for 1 hour and thereafter, the reaction solution was allowed to stand overnight at room temperature. After the reaction solution was again cooled in an ice water bath, 1,800 g of 16.7% ammonium chloride aqueous solution (NH4Cl 300 g+H2O 1,500 g) was added thereto at a temperature not in excess of 30° C. After separation, 1,000 g of chloroform was added to the organic layer, which was washed three times using 1,000 g of water. Thereafter, the solvent was distilled off under reduced pressure by means of a rotary evaporator and the resulting oily residue was recrystallized, isolating tris(4-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate of 99% purity in an amount of 141 g (yield 45%). was added dropwise at less 30° C Reaction mixture Reaction mixture was further ripened for 1 hour to stand overnight at room temperature After the reaction solution was again cooled in an ice water bath excess of 30° C After separation, 1,000 g of chloroform was added to the organic layer, which was washed three times Thereafter, the solvent was distilled off under reduced pressure by means of a rotary evaporator the resulting oily residue was recrystallized

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

Procedure: A solution of 20.2 g (0.10 mol) of diphenyl sulfoxide in 200 g of methylene chloride was cooled on an ice bath. To the solution, 5.3 g (0.052 mol) of triethylamine was added and 32.6 g (0.30 mol) of trimethylsilyl chloride was dropwised at 0° to 20° C. Stirring was continued at 0° to 10° C. for 15 minutes. To this solution, a Grignard reagent which was conventionally prepared from 55.4 g (0.30 mol) of 4-tert-butoxychlorobenzene, 7.3 g (0.30 mol) of magnesium, and 90 g of THF was dropwised at 0° to 10 ° C. Stirring was continued at 0° to 10° C. for 30 minutes. 500 g of 20% ammonium chloride aqueous solution was added to the reaction mixture. To the organic layer was added 1,000 g of chloroform. The organic layer was once washed with 200 g of water and the solvent was evaporated. The residue was purified by recrystalization, isolating 26.6 g (yield 72%) of (4-tert-butoxyphenyl)diphenylsulfonium chloride with 98% purity. was dropwised at 0° to 20° C was dropwised at 0° to 10 ° C Stirring was continued at 0° to 10° C. for 30 minutes The organic layer was once washed with 200 g of water the solvent was evaporated The residue was purified by recrystalization

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

Procedure: A solution of 17.8 g (0.052 mol) of bis(4-tertbutoxyphenyl) sulfoxide in 52 g of THF was cooled on an ice bath. To the solution, 5.3 g (0.052 mol) of triethylamine was added and 14.1 g (0.13 mol) of trimethylsilyl chloride was dropwised at 0° to 10° C. Stirring was continued at 0 to 10° C. for 30 minutes. To this solution, a Grignard reagent which was conventionally prepared from 24.0 g (0.13 mol) of 4-tert-butoxychlorobenzene, 3.2 g (0.13 mol) of magnesium, and 40 g of THF was dropwised at 0° to 10° C. Stirring was continued at 0° to 10° C. for 30 minutes. 300 g of 20% ammonium chloride aqueous solution was added to the reaction mixture. To the organic layer was added 500 g of chloroform. The organic layer was washed twice with 200 g of water and the solvent was evaporated and residue was purifie by column chromatography (silica gel, eluent: chloroform/methanol), isolating 9.3 g (yield 35%) of tris(4-tert-butoxyphenyl)sulfonium chloride with 99% purity. was dropwised at 0° to 10° C was dropwised at 0° to 10° C Stirring was continued at 0° to 10° C. for 30 minutes The organic layer was washed twice with 200 g of water the solvent was evaporated

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

Procedure: A solution of 17.8 g (0.052 mol) of bis(4-tertbutoxyphenyl) sulfoxide in 52 g of THF was cooled on an ice bath. To the solution, 5.3 g (0.052 mol) of triethylamine was added and 14.1 g (0.13 mol) of trimethylsilyl chloride was dropwised at 0° to 10° C. Stirring was continued at 0 to 10° C. for 30 minutes. To this solution, a Grignard reagent which was conventionally prepared from 24.0 g (0.13 mol) of 4-tert-butoxychlorobenzene, 3.2 g (0.13 mol) of magnesium, and 40 g of THF was dropwised at 0° to 10° C. Stirring was continued at 0° to 10° C. for 30 minutes. 300 g of 20% ammonium chloride aqueous solution was added to the reaction mixture. To the organic layer was added 500 g of chloroform. The organic layer was washed twice with 200 g of water and the solvent was evaporated and residue was purifie by column chromatography (silica gel, eluent: chloroform/methanol), isolating 9.3 g (yield 35%) of tris(4-tert-butoxyphenyl)sulfonium chloride with 99% purity. was dropwised at 0° to 10° C was dropwised at 0° to 10° C Stirring was continued at 0° to 10° C. for 30 minutes The organic layer was washed twice with 200 g of water the solvent was evaporated