2-sulfanylphenol

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:

反応条件: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 60% sodium hydride in mineral oil (7.0 g, 0.20 mol) and acetonitrile (200 mL) under a nitrogen atmosphere was added dropwise a solution of 2,6-di-t-butyl-4-mercaptophenol (A) (53.7 g, 0.23 mol, 90%) in acetonitrile (100 mL) over a 1 h period. The reaction mixture was stirred at 25° C. for an additional hour to ensure complete anion generation. To the mercaptophenol anion was added a solution of methyl (2S)-2-(phenylsulfonyloxy)propanate (50 g, 0.20 mol, 12) in acetonitrile (100 mL) dropwise over a 1 h period. Upon addition of methyl (2S)-2-(phenylsulfonyloxy)propanate a white precipitate was observed. The reaction mixture was allowed to stir at 25° C. overnight. The mixture was worked-up by filtration through a coarse sintered glass funnel containing was Celite®. The solvent was removed by rotary evaporation to afford a smelly yellow oil. Purification by flash chromatography on silica gel (EM silica gel 60, 0.040-0.063 partical size, 230-400 Mesh, column size: 10 cm diameter×30 cm length) using hexane and ethyl acetate (9:1) afforded 51.3 g (81%) of methyl (2R)-2-(3,5-di-t-butyl-4-hydroxyphenyl)thiopropanoate (31) as a thick oil: 1H NMR (CDCl3) δ1.42-1.45 (m, 21 H), 3.60-3.68 (q, J=7.2 Hz, 1 H), 3.67 (s, 3 H), 5.33 (s, --OH, 1 H), 7.29 (s, 2 H); 13C NMR (CDCl3) δ173.3, 154.6, 136.6, 131.8, 122.0, 52.0, 46.0, 34.3, 30.2, 17.4; IR (neat) 3635 (s), 2958 (vs), 2875 (s), 1737 (vs), 1426 (vs), 1237 (vs), 1160 (vs), 855 (w), 774 (w) cm-1. to stir at 25° C. overnight The mixture was worked-up by filtration through a coarse sintered glass funnel containing The solvent was removed by rotary evaporation to afford a smelly yellow oil Purification by flash chromatography on silica gel (EM silica gel 60, 0.040-0.063 partical size, 230-400 Mesh, column size: 10 cm diameter×30 cm length)

反応条件: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 60% sodium hydride in mineral oil (7.0 g, 0.20 mol) and acetonitrile (200 mL) under a nitrogen atmosphere was added dropwise a solution of 2,6-di-t-butyl-4-mercaptophenol (A) (53.7 g, 0.23 mol, 90%) in acetonitrile (100 mL) over a 1 h period. The reaction mixture was stirred at 25° C. for an additional hour to ensure complete anion generation. To the mercaptophenol anion was added a solution of methyl (2S)-2-(phenylsulfonyloxy)propanate (50 g, 0.20 mol, 12) in acetonitrile (100 mL) dropwise over a 1 h period. Upon addition of methyl (2S)-2-(phenylsulfonyloxy)propanate a white precipitate was observed. The reaction mixture was allowed to stir at 25° C. overnight. The mixture was worked-up by filtration through a coarse sintered glass funnel containing was Celite®. The solvent was removed by rotary evaporation to afford a smelly yellow oil. Purification by flash chromatography on silica gel (EM silica gel 60, 0.040-0.063 partical size, 230-400 Mesh, column size: 10 cm diameter×30 cm length) using hexane and ethyl acetate (9:1) afforded 51.3 g (81%) of methyl (2R)-2-(3,5-di-t-butyl-4-hydroxyphenyl)thiopropanoate (31) as a thick oil: 1H NMR (CDCl3) δ1.42-1.45 (m, 21 H), 3.60-3.68 (q, J=7.2 Hz, 1 H), 3.67 (s, 3 H), 5.33 (s, --OH, 1 H), 7.29 (s, 2 H); 13C NMR (CDCl3) δ173.3, 154.6, 136.6, 131.8, 122.0, 52.0, 46.0, 34.3, 30.2, 17.4; IR (neat) 3635 (s), 2958 (vs), 2875 (s), 1737 (vs), 1426 (vs), 1237 (vs), 1160 (vs), 855 (w), 774 (w) cm-1. to stir at 25° C. overnight The mixture was worked-up by filtration through a coarse sintered glass funnel containing The solvent was removed by rotary evaporation to afford a smelly yellow oil Purification by flash chromatography on silica gel (EM silica gel 60, 0.040-0.063 partical size, 230-400 Mesh, column size: 10 cm diameter×30 cm length)

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

実験手順: To the refluxing solution of 75 g of 2-hydroxythiophenol [J. Pharm. Sci. 61, 2 (1972)] in 660 ml of acetone is added 42 g of potassium carbonate, followed by the dropwise addition of the solution of 33.5 g of 3,4-dibromobutyronitrile in 50 ml of acetone while stirring. After 30 minutes refluxing, a second, third, and fourth addition of 42 g potassium carbonate and 33.5 g of 3,4-dibromobutyronitrile is made. The whole mixture is refluxed for 20 hours, cooled and filtered. The filtrate is evaporated and the residue distilled in a bulb to bulb apparatus at 185° and 0.5 mmHg, to yield the 2-(1,4-benzoxathian-2-yl)-acetonitrile. After 30 minutes refluxing The whole mixture is refluxed for 20 hours cooled filtered The filtrate is evaporated the residue distilled in a bulb to bulb apparatus at 185°

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

実験手順: (S)-tert-Butyl (1-(5-iodo-4-oxo-3-phenyl-3,4-dihydropyrrolo[2,1-f][1,2,4]triazin-2-yl)ethyl)carbamate (250 mg, 0.52 mmol) was treated with 2-mercaptophenol (80 μl, 0.80 mmol), potassium carbonate (110 mg, 0.8 mmol) and copper(I) iodide (150 mg, 0.79 mmol) according to the method described in Preparation 44. The crude was purified using SP1® Purification System (0%-25%, hexane-ethyl acetate) to give 252 mg (64% yield) to the title compound as an oil. described in Preparation 44 The crude was purified SP1® Purification System (0%-25%, hexane-ethyl acetate)