[chloro(difluoro)methyl] thiohypochlorite

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

Procedure: To the solution of 1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-5-hydroxypyrazole (12.0 g, 37.3 mmol.) and pyridine (3.25 g, 41.0 mmol) in dichloromethane at −50-−60 C. was added chlorodifluoromethanesulfenyl chloride (8.1 g, 46.6 mmol). The resulting solution was gradually warmed up to room temperature. After 20 hr, the organic layer was washed five times with water. It was then washed with brine and dried (Na2SO4) to provide an oil. Upon chromatographic purification of the oil , a total of 11.6 g (26.4 mmol., 71% yield) of the desired product with 97% HPLC puriety was isolated. F-NMR: −30.05 ppm (CCIF2), −63.80 ppm (ArCF3). the organic layer was washed five times with water It was then washed with brine dried (Na2SO4) to provide an oil Upon chromatographic purification of the oil

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

Procedure: To the solution of 1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-5-hydroxypyrazole (12.0 g, 37.3 mmol.) and pyridine (3.25 g, 41.0 mmol) in dichloromethane at −50-−60 C. was added chlorodifluoromethanesulfenyl chloride (8.1 g, 46.6 mmol). The resulting solution was gradually warmed up to room temperature. After 20 hr, the organic layer was washed five times with water. It was then washed with brine and dried (Na2SO4) to provide an oil. Upon chromatographic purification of the oil , a total of 11.6 g (26.4 mmol., 71% yield) of the desired product with 97% HPLC puriety was isolated. F-NMR: −30.05 ppm (CCIF2), −63.80 ppm (ArCF3). the organic layer was washed five times with water It was then washed with brine dried (Na2SO4) to provide an oil Upon chromatographic purification of the oil

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

Procedure: To the solution of 1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-5-hydroxypyrazole (12.0 g, 37.3 mmol.) and pyridine (3.25 g, 41.0 mmol) in dichloromethane at −50 to −60 C was added chlorodifluoromethanesulfenyl chloride (8.1 g, 46.6 mmol). The resulting solution was gradually warmed up to room temperature. After 20 hr, the organic layer was washed five times with water. It was then washed with brine and dried (Na2SO4) to provide an oil. Upon chromatographic purification of the oil, a total of 11.6 g (26.4 mmol., 71% yield) of the desired product with 97% HPLC purity was isolated. F-NMR: −30.05 ppm (CClF2), −63.80 ppm (ArCF3). the organic layer was washed five times with water It was then washed with brine dried (Na2SO4) to provide an oil Upon chromatographic purification of the oil

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

Procedure: To the solution of 1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-5-hydroxypyrazole (12.0 g, 37.3 mmol.) and pyridine (3.25 g, 41.0 mmol) in dichloromethane at −50 to −60 C was added chlorodifluoromethanesulfenyl chloride (8.1 g, 46.6 mmol). The resulting solution was gradually warmed up to room temperature. After 20 hr, the organic layer was washed five times with water. It was then washed with brine and dried (Na2SO4) to provide an oil. Upon chromatographic purification of the oil, a total of 11.6 g (26.4 mmol., 71% yield) of the desired product with 97% HPLC purity was isolated. F-NMR: −30.05 ppm (CClF2), −63.80 ppm (ArCF3). the organic layer was washed five times with water It was then washed with brine dried (Na2SO4) to provide an oil Upon chromatographic purification of the oil

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

Procedure: To the solution of 1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-5-hydroxypyrazole (12.0 g, 37.3 mmol.) and pyridine (3.25 g, 41.0 mmol) in dichloromethane at −50 to −60 C was added chlorodifluoromethanesulfenyl chloride (8.1 g, 46.6 mmol). The resulting solution was gradually warmed up to room temperature. After 20 hr, the organic layer was washed five times with water. It was then washed with brine and dried (Na2SO4) to provide an oil. Upon chromatographic purification of the oil, a total of 11.6 g (26.4 mmol., 71% yield) of the desired product with 97% HPLC purity was isolated. F-NMR: −30.05 ppm (CClF2), −63.80 ppm (ArCF3). the organic layer was washed five times with water It was then washed with brine dried (Na2SO4) to provide an oil Upon chromatographic purification of the oil

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

Procedure: To the solution of 1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-5-hydroxypyrazole (12.0 g, 37.3 mmol.) and pyridine (3.25 g, 41.0 mmol) in dichloromethane at −50 to −60 C was added chlorodifluoromethanesulfenyl chloride (8.1 g, 46.6 mmol). The resulting solution was gradually warmed up to room temperature. After 20 hr, the organic layer was washed five times with water. It was then washed with brine and dried (Na2SO4) to provide an oil. Upon chromatographic purification of the oil, a total of 11.6 g (26.4 mmol., 71% yield) of the desired product with 97% HPLC purity was isolated. F-NMR: −30.05 ppm (CClF2), −63.80 ppm (ArCF3). the organic layer was washed five times with water It was then washed with brine dried (Na2SO4) to provide an oil Upon chromatographic purification of the oil

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

Procedure: To the solution of 1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-5-hydroxypyrazole (12.0 g, 37.3 mmol.) and pyridine (3.25 g, 41.0 mmol) in dichloromethane at −50-−60 C. was added chlorodifluoromethanesulfenyl chloride (8.1 g, 46.6 mmol). The resulting solution was gradually warmed up to room temperature. After 20 hr, the organic layer was washed five times with water. It was then washed with brine and dried (Na2SO4) to provide an oil. Upon chromatographic purification of the oil , a total of 11.6 g (26.4 mmol., 71% yield) of the desired product with 97% HPLC puriety was isolated. F-NMR: −30.05 ppm (CCIF2), −63.80 ppm (ArCF3). the organic layer was washed five times with water It was then washed with brine dried (Na2SO4) to provide an oil Upon chromatographic purification of the oil