2-(trifluoromethylsulfanyl)aniline

反応条件: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 25.53 g of tin(II) chloride dihydrate in 40 ml of concentrated hydrochloric acid was added dropwise to a stirred solution of 5.05 g of 2-nitrophenyl trifluoromethyl sulfide, obtained according to Example 1, in 30 ml of ethanol. After the addition had ended, the mixture was heated to 100° C. and stirred at this temperature for 1.5 hours. The mixture was cooled, ethanol was evaporated off under reduced pressure, and the residue was poured into a mixture of 150 g of ice and 150 ml of 40% strength by weight aqueous sodium hydroxide solution. The product was extracted with ether. The combined ether extracts were dried over magnesium sulfate and concentrated under reduced pressure. Vacuum distillation of the residue gave 3.31 g (75.7% of theory) of 2-aminophenyl trifluoromethyl sulfide (boiling point 102-104° C. at 50 mbar, melting point: 30-31° C.). obtained After the addition The mixture was cooled ethanol was evaporated off under reduced pressure the residue was poured into a mixture of 150 g of ice and 150 ml of 40% strength by weight aqueous sodium hydroxide solution The product was extracted with ether The combined ether extracts were dried over magnesium sulfate concentrated under reduced pressure Vacuum distillation of the residue

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2-(trifluoromethylthio)benzenamine (1 g, 5.18 mmol) prepared in accordance with the method described in J. Fluorin. Chem. 1994, 69, 207 to 212, 5 ml of glacial acetic acid, and 3 ml of 50% sulfuric acid were charged into a 50-ml eggplant flask equipped with a stirrer, were dissolved, and then the mixture was cooled to 0° C. on an ice bath. To the mixture, 1 ml of an aqueous solution of sodium nitrite (0.43 g, 6.22 mmol) was added and the mixture was stirred for 1.5 hours. Then, 1 ml of an aqueous solution of sodium iodide (0.95 g, 6.3 mmol) was added dropwise at 0° C. and the mixture was stirred for 30 minutes. After completion of the reaction, the reaction solution was gradually heated to room temperature and added to water, and the solution was extracted three times with ether. The obtained organic layer was washed three times with water, two times with a saturated sodium bisulfite aqueous solution, and three times with water, dried over anhydrous sodium sulfate, and concentrated to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (Hexane 100) to give target (trifluoromethyl)(2-iodophenyl)sulfide (1.5 g, 95%) as a yellow oil. equipped with a stirrer were dissolved the mixture was stirred for 30 minutes After completion of the reaction the reaction solution was gradually heated to room temperature the solution was extracted three times with ether The obtained organic layer was washed three times with water, two times with a saturated sodium bisulfite aqueous solution, and three times with water dried over anhydrous sodium sulfate concentrated to obtain a crude product The obtained crude product was purified by silica gel column chromatography (Hexane 100)

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2-(trifluoromethylthio)benzenamine (1 g, 5.18 mmol) prepared in accordance with the method described in J. Fluorin. Chem. 1994, 69, 207 to 212, 5 ml of glacial acetic acid, and 3 ml of 50% sulfuric acid were charged into a 50-ml eggplant flask equipped with a stirrer, were dissolved, and then the mixture was cooled to 0° C. on an ice bath. To the mixture, 1 ml of an aqueous solution of sodium nitrite (0.43 g, 6.22 mmol) was added and the mixture was stirred for 1.5 hours. Then, 1 ml of an aqueous solution of sodium iodide (0.95 g, 6.3 mmol) was added dropwise at 0° C. and the mixture was stirred for 30 minutes. After completion of the reaction, the reaction solution was gradually heated to room temperature and added to water, and the solution was extracted three times with ether. The obtained organic layer was washed three times with water, two times with a saturated sodium bisulfite aqueous solution, and three times with water, dried over anhydrous sodium sulfate, and concentrated to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (Hexane 100) to give target (trifluoromethyl)(2-iodophenyl)sulfide (1.5 g, 95%) as a yellow oil. equipped with a stirrer were dissolved the mixture was stirred for 30 minutes After completion of the reaction the reaction solution was gradually heated to room temperature the solution was extracted three times with ether The obtained organic layer was washed three times with water, two times with a saturated sodium bisulfite aqueous solution, and three times with water dried over anhydrous sodium sulfate concentrated to obtain a crude product The obtained crude product was purified by silica gel column chromatography (Hexane 100)

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2-(trifluoromethylthio)benzenamine (1 g, 5.18 mmol) prepared in accordance with a method described in J. Fluorin. Chem. 1994, 69, 207 to 212, 5 ml of glacial acetic acid, and 3 ml of 50% sulfuric acid were added into a 50-ml eggplant flask equipped with a stirrer, and were dissolved. Then the mixture was cooled to 0° C. on an ice bath. To the mixture, 1 ml of an aqueous solution of sodium nitrite (0.43 g, 6.22 mmol) was added and the mixture was stirred for 1.5 hours. 1 ml of an aqueous solution of sodium iodide (0.95 g, 6.3 mmol) was added dropwise at 0° C. and the mixture was stirred for 30 minutes. After completion of the reaction, the reaction solution was gradually heated to room temperature and added to water, and the solution was extracted three times with ether. The obtained organic layer was washed three times with water, two times with a saturated sodium bisulfite aqueous solution, and three times with water, dried over anhydrous sodium sulfate, and concentrated to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (Hexane 100) to give target (trifluoromethyl)-(2-iodophenyl)sulfide (1.5 g, 95%) as a yellow oil. equipped with a stirrer were dissolved the mixture was stirred for 30 minutes After completion of the reaction the reaction solution was gradually heated to room temperature the solution was extracted three times with ether The obtained organic layer was washed three times with water, two times with a saturated sodium bisulfite aqueous solution, and three times with water dried over anhydrous sodium sulfate concentrated to obtain a crude product The obtained crude product was purified by silica gel column chromatography (Hexane 100)

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2-(trifluoromethylthio)benzenamine (1 g, 5.18 mmol) prepared in accordance with a method described in J. Fluorin. Chem. 1994, 69, 207 to 212, 5 ml of glacial acetic acid, and 3 ml of 50% sulfuric acid were added into a 50-ml eggplant flask equipped with a stirrer, and were dissolved. Then the mixture was cooled to 0° C. on an ice bath. To the mixture, 1 ml of an aqueous solution of sodium nitrite (0.43 g, 6.22 mmol) was added and the mixture was stirred for 1.5 hours. 1 ml of an aqueous solution of sodium iodide (0.95 g, 6.3 mmol) was added dropwise at 0° C. and the mixture was stirred for 30 minutes. After completion of the reaction, the reaction solution was gradually heated to room temperature and added to water, and the solution was extracted three times with ether. The obtained organic layer was washed three times with water, two times with a saturated sodium bisulfite aqueous solution, and three times with water, dried over anhydrous sodium sulfate, and concentrated to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (Hexane 100) to give target (trifluoromethyl)-(2-iodophenyl)sulfide (1.5 g, 95%) as a yellow oil. equipped with a stirrer were dissolved the mixture was stirred for 30 minutes After completion of the reaction the reaction solution was gradually heated to room temperature the solution was extracted three times with ether The obtained organic layer was washed three times with water, two times with a saturated sodium bisulfite aqueous solution, and three times with water dried over anhydrous sodium sulfate concentrated to obtain a crude product The obtained crude product was purified by silica gel column chromatography (Hexane 100)

反応条件: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 25.53 g of tin(II) chloride dihydrate in 40 ml of concentrated hydrochloric acid was added dropwise to a stirred solution of 5.05 g of 2-nitrophenyl trifluoromethyl sulfide, obtained according to Example 1, in 30 ml of ethanol. After the addition had ended, the mixture was heated to 100° C. and stirred at this temperature for 1.5 hours. The mixture was cooled, ethanol was evaporated off under reduced pressure, and the residue was poured into a mixture of 150 g of ice and 150 ml of 40% strength by weight aqueous sodium hydroxide solution. The product was extracted with ether. The combined ether extracts were dried over magnesium sulfate and concentrated under reduced pressure. Vacuum distillation of the residue gave 3.31 g (75.7% of theory) of 2-aminophenyl trifluoromethyl sulfide (boiling point 102-104° C. at 50 mbar, melting point: 30-31° C.). obtained After the addition The mixture was cooled ethanol was evaporated off under reduced pressure the residue was poured into a mixture of 150 g of ice and 150 ml of 40% strength by weight aqueous sodium hydroxide solution The product was extracted with ether The combined ether extracts were dried over magnesium sulfate concentrated under reduced pressure Vacuum distillation of the residue