3,5-DICHLOROTHIOANISOLE

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

Procedure: A 4-necked, 1-liter flask equipped with a stirrer, a thermometer and a condenser tube was charged with 181.5 g (1.00 mole) of 1,3,5-trichlorobenzene and 67.9 g (0.10 mole) of an aqueous solution of 50 wt % tetra-n-butylphosphonium bromide. 233.6 g (1.00 mole) of an aqueous solution of 30 wt % sodium thiomethoxide was added dropwise at 80° C. over a period of 6 hours. After addition, the mixture was reacted at the same temperature for 10 hours. After completion of reaction, 191.9 g of a crude 1-methylthio-3,5-dichlorobenzene was obtained by separation procedure. A 4-necked, 1-liter flask equipped with a stirrer After addition the mixture was reacted at the same temperature for 10 hours After completion of reaction

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

Procedure: A 4-necked, 1-liter flask equipped with a stirrer, a thermometer and a condenser tube was charged with 181.5 g (1.00 mole) of 1,3,5-trichlorobenzene and 67.9 g (0.10 mole) of an aqueous solution of 50 wt % tetra-n-butylphosphonium bromide. 233.6 g (1.00 mole) of an aqueous solution of 30 wt % sodium thiomethoxide was added dropwise at 80° C. over a period of 6 hours. After addition, the mixture was reacted at the same temperature for 10 hours. After completion of reaction, 191.9 g of a crude 1-methylthio-3,5-dichlorobenzene was obtained by separation procedure. A 4-necked, 1-liter flask equipped with a stirrer After addition the mixture was reacted at the same temperature for 10 hours After completion of reaction

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

Procedure: To a stirred solution of (3,5-dichlorophenyl)(methyl)sulfane (1.0 g, 5.1 mmol) in THF (15 mL), n-BuLi (1.6 M in THF, 4.8 mL, 7.7 mmol) was added dropwise at −78° C. and stirred for 1 h at the same temperature. A solution of DMF (0.6 mL, 7.7 mmol) in THF (3 mL) was added slowly at −78° C. and stirred for 1 h. The reaction mixture was quenched with saturated NH4Cl aq. (50 mL) and extracted with EtOAc (2×30 mL). The combined organic layers were washed with water (30 mL), brine (30 mL), dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified by column chromatography (silica gel, 20% EtOAc/hexane as eluent) to afford compound A57-1 (1.4 g, 99%) as colorless oil. stirred for 1 h The reaction mixture was quenched with saturated NH4Cl aq. (50 mL) extracted with EtOAc (2×30 mL) The combined organic layers were washed with water (30 mL), brine (30 mL) dried over anhydrous Na2SO4 concentrated under reduced pressure The crude product was purified by column chromatography (silica gel, 20% EtOAc/hexane as eluent) to afford compound A57-1 (1.4 g, 99%) as colorless oil

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

Procedure: A 4-necked, 1-liter flask equipped with a stirrer, a thermometer and a condenser tube was charged with 181.5 g (1.00 mole) of 1,3,5-trichlorobenzene and 67.9 g (0.10 mole) of an aqueous solution of 50 wt % tetra-n-butylphosphonium bromide. 233.6 g (1.00 mole) of an aqueous solution of 30 wt % sodium thiomethoxide was added dropwise at 80° C. over a period of 6 hours. After addition, the mixture was reacted at the same temperature for 10 hours. After completion of reaction, 191.9 g of a crude 1-methylthio-3,5-dichlorobenzene was obtained by separation procedure. A 4-necked, 1-liter flask equipped with a stirrer After addition the mixture was reacted at the same temperature for 10 hours After completion of reaction