5-bromo-2-fluorobenzenecarbothioamide

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

Procedure: A mixture of 5-bromo-2-fluoro-benzenecarbothioamide (11.8 mmol, 2840 mg) and ethyl bromopyruvate (1.05 equiv., 12.4 mmol, 1.56 mL) in ethanol (30 mL) was heated at 80° C. overnight. The mixture was concentrated and the residue was purified on silica eluted with 0 to 20% EtOAc in Heptane to afford ethyl 2-(5-bromo-2-fluoro-phenyl)thiazole-4-carboxylate (2960 mg, 76.14% Yield) as a clear oil. The mixture was concentrated the residue was purified on silica eluted with 0 to 20% EtOAc in Heptane

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 5-bromo-2-fluoro-benzonitrile (12.4 mmol, 2470 mg) in pyridine (6.5 mL) was treated with ammonium sulfide (40 mass % in water, 1.1 equiv., 13.6 mmol, 2.32 mL) and triethylamine (1.1 equiv., 13.6 mmol, 1.90 mL). The reaction mixture was heated at 50° C. for 3 hours, then cooled to room temperature. The reaction mixture was partitioned between EtOAc and water. The organic later was washed with water (3×), and brine (3×), dried with MgSO4, then concentrated. The residue was purified on silica eluted with 0 to 50% EtOAc in Heptane to provide 5-bromo-2-fluoro-benzenecarbothioamide (2.84 g, 94% yield). cooled to room temperature The reaction mixture was partitioned between EtOAc and water The organic later was washed with water (3×), and brine (3×) dried with MgSO4 concentrated The residue was purified on silica eluted with 0 to 50% EtOAc in Heptane

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 5-bromo-2-fluoro-benzonitrile (12.4 mmol, 2470 mg) in pyridine (6.5 mL) was treated with ammonium sulfide (40 mass % in water, 1.1 equiv., 13.6 mmol, 2.32 mL) and triethylamine (1.1 equiv., 13.6 mmol, 1.90 mL). The reaction mixture was heated at 50° C. for 3 hours, then cooled to room temperature. The reaction mixture was partitioned between EtOAc and water. The organic later was washed with water (3×), and brine (3×), dried with MgSO4, then concentrated. The residue was purified on silica eluted with 0 to 50% EtOAc in Heptane to provide 5-bromo-2-fluoro-benzenecarbothioamide (2.84 g, 94% yield). cooled to room temperature The reaction mixture was partitioned between EtOAc and water The organic later was washed with water (3×), and brine (3×) dried with MgSO4 concentrated The residue was purified on silica eluted with 0 to 50% EtOAc in Heptane

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

Procedure: A mixture of 5-bromo-2-fluoro-benzenecarbothioamide (11.8 mmol, 2840 mg) and ethyl bromopyruvate (1.05 equiv., 12.4 mmol, 1.56 mL) in ethanol (30 mL) was heated at 80° C. overnight. The mixture was concentrated and the residue was purified on silica eluted with 0 to 20% EtOAc in Heptane to afford ethyl 2-(5-bromo-2-fluoro-phenyl)thiazole-4-carboxylate (2960 mg, 76.14% Yield) as a clear oil. The mixture was concentrated the residue was purified on silica eluted with 0 to 20% EtOAc in Heptane

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 5-bromo-2-fluoro-benzonitrile (12.4 mmol, 2470 mg) in pyridine (6.5 mL) was treated with ammonium sulfide (40 mass % in water, 1.1 equiv., 13.6 mmol, 2.32 mL) and triethylamine (1.1 equiv., 13.6 mmol, 1.90 mL). The reaction mixture was heated at 50° C. for 3 hours, then cooled to room temperature. The reaction mixture was partitioned between EtOAc and water. The organic later was washed with water (3×), and brine (3×), dried with MgSO4, then concentrated. The residue was purified on silica eluted with 0 to 50% EtOAc in Heptane to provide 5-bromo-2-fluoro-benzenecarbothioamide (2.84 g, 94% yield). cooled to room temperature The reaction mixture was partitioned between EtOAc and water The organic later was washed with water (3×), and brine (3×) dried with MgSO4 concentrated The residue was purified on silica eluted with 0 to 50% EtOAc in Heptane