4-bromo-3-methylbenzenethiol

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

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

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 4-bromo-3-methylbenzenethiol (5.47 g, 26.9 mmol) in DMF (25 mL) was added NaH (0.743 g, 32.3 mmol) at RT. After 15 minutes at RT, the solution was cooled to 0° C. and iodomethane (2.02 ml, 32.3 mmol) was added. The cooling bath was removed and the mixture was allowed to warm up to RT. After 1 hour, water was added and the mixture was extracted with EtOAc (3×). The combined organic layers were dried over anhydrous sodium sulfate, filtered and concentrated to give 5.81 g of (4-bromo-3-methylphenyl)(methyl)sulfane as a pale yellow oil. The cooling bath was removed to warm up to RT After 1 hour water was added the mixture was extracted with EtOAc (3×) The combined organic layers were dried over anhydrous sodium sulfate filtered concentrated

Conditions: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of S-4-bromo-3-methylphenyl dimethylcarbamothioate (4.56 g, 16.6 mmol) and potassium hydroxide (3.27 g, 58.2 mmol) in MeOH was heated at 90° C. for 1 hour. The mixture was cooled to RT and concentrated. The residue was redissolved in DCM and aqueous sodium bicarbonate (sat.) and the layers were separated. The organic layer was dried over sodium sulfate, filtered and concentrated. The crude material was purified by silica gel chromatography (100% hexanes) to afford 2.84 g of 4-bromo-3-methylbenzenethiol as a pale yellow oil. The mixture was cooled to RT concentrated The residue was redissolved in DCM aqueous sodium bicarbonate (sat.) and the layers were separated The organic layer was dried over sodium sulfate filtered concentrated The crude material was purified by silica gel chromatography (100% hexanes)

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

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

Procedure: Prepared analogous to Example 122 from 6-(4-bromobutoxy)-3,4-dihydro-carbostyril (m.p. 142°-147° C.) and 4-bromo-3-methyl-thiophenol.

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

Procedure: Prepared analogous to Example 122 from 6-(4-bromobutoxy)-carbostyril (m.p. 189°-199° C.) and 3-methyl-4-bromo-thiophenol.

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

Procedure: Prepared analogous to Example 122 from 6-(4-bromobutoxy)-carbostyril (m.p. 189°-199° C.) and 3-methyl-4-bromo-thiophenol.

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

Procedure: Prepared analogously to Example 1 from 6-(4-chlorobutoxy)-4,4-dimethyl-4H-3,1-benzoxazin-2-one and 4-bromo-3-methyl-thiophenol.

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 4-bromo-3-methylbenzenethiol (5.47 g, 26.9 mmol) in DMF (25 mL) was added NaH (0.743 g, 32.3 mmol) at RT. After 15 minutes at RT, the solution was cooled to 0° C. and iodomethane (2.02 ml, 32.3 mmol) was added. The cooling bath was removed and the mixture was allowed to warm up to RT. After 1 hour, water was added and the mixture was extracted with EtOAc (3×). The combined organic layers were dried over anhydrous sodium sulfate, filtered and concentrated to give 5.81 g of (4-bromo-3-methylphenyl)(methyl)sulfane as a pale yellow oil. The cooling bath was removed to warm up to RT After 1 hour water was added the mixture was extracted with EtOAc (3×) The combined organic layers were dried over anhydrous sodium sulfate filtered concentrated

Conditions: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of S-4-bromo-3-methylphenyl dimethylcarbamothioate (4.56 g, 16.6 mmol) and potassium hydroxide (3.27 g, 58.2 mmol) in MeOH was heated at 90° C. for 1 hour. The mixture was cooled to RT and concentrated. The residue was redissolved in DCM and aqueous sodium bicarbonate (sat.) and the layers were separated. The organic layer was dried over sodium sulfate, filtered and concentrated. The crude material was purified by silica gel chromatography (100% hexanes) to afford 2.84 g of 4-bromo-3-methylbenzenethiol as a pale yellow oil. The mixture was cooled to RT concentrated The residue was redissolved in DCM aqueous sodium bicarbonate (sat.) and the layers were separated The organic layer was dried over sodium sulfate filtered concentrated The crude material was purified by silica gel chromatography (100% hexanes)

Conditions: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of S-4-bromo-3-methylphenyl dimethylcarbamothioate (4.56 g, 16.6 mmol) and potassium hydroxide (3.27 g, 58.2 mmol) in MeOH was heated at 90° C. for 1 hour. The mixture was cooled to RT and concentrated. The residue was redissolved in DCM and aqueous sodium bicarbonate (sat.) and the layers were separated. The organic layer was dried over sodium sulfate, filtered and concentrated. The crude material was purified by silica gel chromatography (100% hexanes) to afford 2.84 g of 4-bromo-3-methylbenzenethiol as a pale yellow oil. The mixture was cooled to RT concentrated The residue was redissolved in DCM aqueous sodium bicarbonate (sat.) and the layers were separated The organic layer was dried over sodium sulfate filtered concentrated The crude material was purified by silica gel chromatography (100% hexanes)