3-bromo-4-methylbenzenethiol

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: A solution of 3-bromo-4-methyl-benzenethiol (1.27 g; 6.25 mmol) in anhydrous DMF (12.5 ml) was treated with sodium hydride (300 mg; 7.5 mmol). Then reaction mixture was stirred at RT for 15 minutes, then the treated with 1-iodopropane (0.73 ml; 7.5 mmol). The reaction was stirred for 24 hours, before being quenched by dropwise addition of water. EtOAc was added and the layers separated. The organic layer was washed with brine, dried on MgSO4, filtered and concentrated under reduced pressure. The residue was dissolved in MeOH (13 mL), cooled to 0° C. and treated with a 0.5 M solution of sodium (meta)periodate in water (12.5 ml; 6.24 mmol). After stirring for 24 hours at RT, EtOAc and water were added and the phases separated and the organic phase was dried over MgSO4 and concentrated under reduced pressure. The resulting residue was purified by flash column chromatography (silica), eluting with cyclohexane containing increasing amounts of EtOAc to give the title compound as a yellow sticky solid. Then reaction mixture The reaction was stirred for 24 hours before being quenched by dropwise addition of water EtOAc was added the layers separated The organic layer was washed with brine dried on MgSO4 filtered concentrated under reduced pressure The residue was dissolved in MeOH (13 mL) cooled to 0° C. After stirring for 24 hours at RT the phases separated the organic phase was dried over MgSO4 concentrated under reduced pressure The resulting residue was purified by flash column chromatography (silica) eluting with cyclohexane containing increasing amounts of EtOAc

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

Procedure: A stirred suspension of NaH (40 mg) in anhydrous DMF (5 mL) was treated with a solution of 3-bromo-4-methylbenzenethiol (200 mg) in anhydrous DMF (3 ml). The reaction mixture was stirred for 30 minutes at RT, then 2-iodo propane (0.14 ml) was added to the reaction mixture and the reaction mixture was heated to 55° C. for 3 hours. The reaction mixture was quenched with ice and extracted with diethylether. The organic layer was dried over sodium sulfate and concentrated under reduced pressure. The crude product was purified by flash chromatography (Silica gel), eluting with hexane, to give the title compounds. the reaction mixture was heated to 55° C. for 3 hours The reaction mixture was quenched with ice extracted with diethylether The organic layer was dried over sodium sulfate concentrated under reduced pressure The crude product was purified by flash chromatography (Silica gel) eluting with hexane

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A cooled (−15° C.) solution of 3-bromo-4-methylaniline (ABCR; 2.0 g) in a 6N solution of HCl in water (30 mL) was treated drop-wise with a solution of sodium nitrite (1.78 g) in water (10 mL). The reaction mixture was stirred for 30 mins. The resulting clear solution was added dropwise to a stirred solution of O-ethyl xanthic acid potassium salt (6.1 g) in water (25 mL). The mixture was then heated to 80° C. for 15 minutes. The mixture was then cooled and extracted with diethyl ether twice. The solvents were evaporated under reduced pressure to give a residue, which was treated with a solution of KOH (6.1 g) in 95% ethanol (55 mL) and heated to reflux for 10 h. The reaction mixture was diluted with water and acidified with conc. HCl to pH 3 and extracted with diethyl ether. The organic layer was washed with water, brine and concentrated under reduced pressure. The crude product was purified by column chromatography (silica gel), eluting with petroleum ether. This product obtained was triturated with hexane to give the title compound (1.5 g, 70%) as an off-white solid. The mixture was then cooled extracted with diethyl ether twice The solvents were evaporated under reduced pressure to give a residue, which heated to reflux for 10 h extracted with diethyl ether The organic layer was washed with water, brine concentrated under reduced pressure The crude product was purified by column chromatography (silica gel) eluting with petroleum ether This product obtained was triturated with hexane

Conditions: temp:0.00; pressure:0.00; stir: