3-methylsulfanylbenzenethiol

反応条件: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 3-(methylthio)benzenethiol as prepared in Preparation 8 (290 g, 1.856 mol) in acetonitrile (3 L) was sparged with nitrogen for 1 hour and then treated with 4-fluorobenzaldehyde (196 mL, 1.856 mol) followed by acetonitrile (150 mL, used as a line wash). The resulting solution was treated with 1,1′,3,3′-tetramethylguanidine (256 mL, 2.04 mol) followed by acetonitrile (150 mL used as a line wash) and heated to 50° C. under nitrogen for 16 hours. The resulting solution was allowed to cool to ambient temperature and diluted with ethyl acetate (3 L) and washed with hydrochloric acid (2M aqueous solution, 1.5 L) and sodium bicarbonate (1 M aqueous solution, 3 L) and brine (half saturated, 1.5 L). The resulting solution was concentrated by distillation at atmospheric pressure to a volume of 2 L and diluted with acetonitrile (3 L). the resulting solution was concentrated by distillation at atmospheric pressure to a volume of 2 L and diluted with acetonitrile (3 L) and concentrated by distillation at atmospheric pressure to a final volume of 3 L. The resulting solution was cooled to ambient temperature and treated with a solution of sodium metabisulfite (377 g, 1.982 mol) in water (3 L). After stirring at ambient temperature for 48 hours the resulting suspension was filtered and the solid collected was washed with water (2-fold 2.5 L) and acetonitrile (2-fold 2.5 L). The solid was suspended in acetonitrile (2 L) and stirred at ambient temperature for 18 hours after which time the suspension was filtered and the solid was washed with acetonitrile (2-fold 1 L) and dried in vacuo at 50° C. to give the title compound as a white solid, 55% yield, 368.7 g. was sparged with nitrogen for 1 hour wash) wash) and to cool to ambient temperature diluted with ethyl acetate (3 L) washed with hydrochloric acid (2M aqueous solution, 1.5 L) and sodium bicarbonate (1 M aqueous solution, 3 L) and brine (half saturated, 1.5 L) The resulting solution was concentrated by distillation at atmospheric pressure to a volume of 2 L diluted with acetonitrile (3 L) the resulting solution was concentrated by distillation at atmospheric pressure to a volume of 2 L diluted with acetonitrile (3 L) concentrated by distillation at atmospheric pressure to a final volume of 3 L The resulting solution was cooled to ambient temperature was filtered the solid collected was washed with water (2-fold 2.5 L) and acetonitrile (2-fold 2.5 L) stirred at ambient temperature for 18 hours after which time the suspension was filtered the solid was washed with acetonitrile (2-fold 1 L) dried in vacuo at 50° C.

反応条件: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of benzene-1,3-dithiol (50 g, 0.351 mmol) in 2-methyltetrahydrofuran (375 mL, 0.351 mmol) was treated with dimethylsulfate (33.3 mL, 0.351 mol) followed by 2-methyltetrahydrofuran (25 mL, used as line wash). The resulting solution was cooled to between 0° C. and 5° C. and sodium hydroxide (2M aqueous solution, 210.6 mL) was added drop wise maintaining the temperature of the reaction mixture below 15° C. followed by 2-methyltetrahydrofuran (25 mL, used as line wash) and heated under nitrogen to 50° C. for 4 hours. After cooling to ambient temperature the resulting solution was treated with tert-butylmethylether (500 mL) and the phases were separated. The organic phase was extracted with sodium hydroxide (2 M aqueous solution, 250 mL) and the combined aqueous phases were cooled to 10° C. and hydrochloric acid (6M aqueous solution, 500 mL) was added whilst maintaining the temperature of the mixture below 25° C. The resulting solution was extracted with tert-butylmethylether (2-fold 250 mL) and the combined organic phases were washed with water (500 mL) and concentrated in vacuo to give the title compound as a yellow oil, 78% yield, 42.9 g. The resulting solution was cooled to between 0° C. and 5° C. wise maintaining the temperature of the reaction mixture below 15° C. After cooling to ambient temperature the resulting solution the phases were separated The organic phase was extracted with sodium hydroxide (2 M aqueous solution, 250 mL) the combined aqueous phases were cooled to 10° C. hydrochloric acid (6M aqueous solution, 500 mL) was added whilst maintaining the temperature of the mixture below 25° C The resulting solution was extracted with tert-butylmethylether (2-fold 250 mL) the combined organic phases were washed with water (500 mL) concentrated in vacuo

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

実験手順: A solution of 3-(methylthio)benzenethiol (19.9 g, 127.3 mmol), prepared as indicated in Rumpf, P., Bull. soc. chim. (1940), 7, pp. 632-4, in acetonitrile (60 mL) was treated with 4-fluorobenzaldehyde (13.4 mL, 127 mmol) followed by potassium carbonate (19.4 g, 140 mmol). After stirring at ambient temperature for 18 hours the suspension was diluted with water (200 mL) and extracted with ethyl acetate (3-fold 300 mL). The combined organic extracts were washed with brine (2-fold 100 mL) and dried (magnesium sulphate) and the solvent removed in vacuo to give a colourless oil. The crude oil was purified by flash column chromatography on silica gel eluting with heptane:ethyl acetate (1:0 changing to 9:1, by volume) to give the title compound as a colourless oil, 33% yield, 10.8 g. extracted with ethyl acetate (3-fold 300 mL) The combined organic extracts were washed with brine (2-fold 100 mL) dried (magnesium sulphate) the solvent removed in vacuo to give a colourless oil The crude oil was purified by flash column chromatography on silica gel eluting with heptane:ethyl acetate (1:0 changing to 9:1, by volume)