benzenesulfinylbenzene

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Diphenyl sulfoxide, 40 g (0.2 mole), was dissolved in 400 g of dichloromethane, which was stirred under ice cooling. At a temperature below 20° C., 65 g (0.6 mole) of trimethylsilyl chloride was added dropwise to the solution, which was allowed to mature for 30 minutes at the temperature. Then, a Grignard reagent which had been prepared from 14.6 g (0.6 mole) of metallic magnesium, 67.5 g (0.6 mole) of chlorobenzene and 168 g of tetrahydrofuran (THF) was added dropwise at a temperature below 20° C. The reaction solution was allowed to mature for one hour, after which 50 g of water at a temperature below 20° C. was added to quench the reaction. To this solution, 150 g of water, 10 g of 12N hydrochloric acid, and 200 g of diethyl ether were further added. The water layer was separated and washed with 100 g of diethyl ether, yielding an aqueous solution of triphenylsulfonium chloride. The compound in aqueous solution form was used in the subsequent reaction without further isolation. was added dropwise at a temperature below 20° C to mature for one hour to quench the reaction The water layer was separated washed with 100 g of diethyl ether

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 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

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:52.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: In a 1 L, round bottom flask equipped with a reflux condenser was combined 1,3,5-trimethylbenzene (40 g, 0.333 mol), diphenylsulfoxide (67.3 g, 0.333 mol) and Eaton's Reagent (160 g). An exothermic reaction occurred. The reaction mixture was maintained at 50-55° C. with stirring for 5 hours. The reaction mixture was then added to deionized water (800 ml). This mixture was stirred for 30 minutes. The mixture was extracted two times with toluene (2×250 ml). The pH of the lower aqueous layer was adjusted to 8-8.5 by addition of a 25% aqueous solution of tetramethylammonium hydroxide (889.6 g). In a 1 L, round bottom flask equipped with a reflux condenser An exothermic reaction This mixture was stirred for 30 minutes The mixture was extracted two times with toluene (2×250 ml) The pH of the lower aqueous layer was adjusted to 8-8.5 by addition of a 25% aqueous solution of tetramethylammonium hydroxide (889.6 g)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 0.055 g (0.5 mmol) of uracil was weighed and placed in a two-neck flask and the atmosphere in the flask was replaced with trifluoromethyl iodide. The following materials were added thereinto: 2.5 g of diphenyl sulfoxide, 0.027 ml of concentrated sulfuric acid, 0.1 ml of a 30% hydrogen peroxide aqueous solution and 0.15 ml of a 1.0 mol/l aqueous solution of iron(II) sulfate, and the mixture was stirred for 20 minutes. During the stirring, the temperature of the reaction system rose up in the range of from 40° C. to 50° C. Thereafter, the resulting solution was cooled to room temperature. Formation of 5-trifluoromethyluracil (19F-NMR yield: 0.47%) was confirmed by 19F-NMR with 2,2,2-trifluoroethanol as an internal standard. placed in a two-neck flask The following materials were added rose up in the range of from 40° C. to 50° C