3-(3-chlorophenyl)-3-methylbutan-2-one

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

実験手順: To a solution of 3-(3-chlorophenyl)-3-methylbutan-2-one (15 g, 76 mmol) in CHCl3 (100 mL) was added chlorosulfuric acid (101 mL, 20 eq) at 0° C. over 2 h. Next SOCl2 (20 mL) was added dropwise to the reaction mixture over 30 min under nitrogen. The reaction mixture was slowly warmed to room temperature and stirred overnight. The mixture was slowly added to ice-water and then extracted with EtOAc. The combined extracts were washed with brine, dried over MgSO4 and evaporated. The residue was purified by chromatography (silica, Hex/EtOAc=9:1 to 4:1) to give 2-chloro-4-(2-methyl-3-oxobutan-2-yl)benzene-1-sulfonyl chloride as a yellow solid (9.8 g, 43%). 1H NMR (400 MHz, CDCl3) δ 8.12 (d, J=8.4 Hz, 1H), 7.54 (s, 1H), 7.37 (d, J=2.2 Hz, 1H), 2.03 (s, 3H), 1.56 (s, 6H). extracted with EtOAc The combined extracts were washed with brine dried over MgSO4 evaporated The residue was purified by chromatography (silica, Hex/EtOAc=9:1 to 4:1)

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

実験手順: To a stirred solution of oxalyl chloride (3.4 mL, 40 mmol, 2 eq) in CH2Cl2 (100 mL) at −78° C. was added DMSO (4.9 mL, 70 mmol, 3.5 eq) dropwide. After stirring 1 h, the reaction mixture was treated dropwise with a solution of 3-(3-chlorophenyl)-3-methylbutan-2-ol (3.98 g, 20 mmol) in CH2Cl2 (100 mL). After stirring 1 h, Et3N (13.9 mL, 100 mmol, 5 eq) was added to the reaction mixture and the resulting mixture was slowly warmed to room temperature. The reaction mixture was partitioned in CH2Cl2 and water. The organic layer was separated, washed with 1N HCl and water, dried over MgSO4 and evaporated in vacuo to give 3-(3-chlorophenyl)-3-methylbutan-2-one (3.9 g, 99%). 1H NMR (400 MHz, CDCl3) δ 7.29 (m, 3H), 7.13 (m, 1H), 1.97 (s, 3H), 1.47 (s, 6H). After stirring 1 h The reaction mixture was partitioned in CH2Cl2 The organic layer was separated washed with 1N HCl and water dried over MgSO4 evaporated in vacuo

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

実験手順: To a solution of 3-(3-chlorophenyl)-3-methylbutan-2-one (15 g, 76 mmol) in CHCl3 (100 mL) was added chlorosulfuric acid (101 mL, 20 eq) at 0° C. over 2 h. Next SOCl2 (20 mL) was added dropwise to the reaction mixture over 30 min under nitrogen. The reaction mixture was slowly warmed to room temperature and stirred overnight. The mixture was slowly added to ice-water and then extracted with EtOAc. The combined extracts were washed with brine, dried over MgSO4 and evaporated. The residue was purified by chromatography (silica, Hex/EtOAc=9:1 to 4:1) to give 2-chloro-4-(2-methyl-3-oxobutan-2-yl)benzene-1-sulfonyl chloride as a yellow solid (9.8 g, 43%). 1H NMR (400 MHz, CDCl3) δ 8.12 (d, J=8.4 Hz, 1H), 7.54 (s, 1H), 7.37 (d, J=2.2 Hz, 1H), 2.03 (s, 3H), 1.56 (s, 6H). extracted with EtOAc The combined extracts were washed with brine dried over MgSO4 evaporated The residue was purified by chromatography (silica, Hex/EtOAc=9:1 to 4:1)

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

実験手順: To a stirred solution of oxalyl chloride (3.4 mL, 40 mmol, 2 eq) in CH2Cl2 (100 mL) at −78° C. was added DMSO (4.9 mL, 70 mmol, 3.5 eq) dropwide. After stirring 1 h, the reaction mixture was treated dropwise with a solution of 3-(3-chlorophenyl)-3-methylbutan-2-ol (3.98 g, 20 mmol) in CH2Cl2 (100 mL). After stirring 1 h, Et3N (13.9 mL, 100 mmol, 5 eq) was added to the reaction mixture and the resulting mixture was slowly warmed to room temperature. The reaction mixture was partitioned in CH2Cl2 and water. The organic layer was separated, washed with 1N HCl and water, dried over MgSO4 and evaporated in vacuo to give 3-(3-chlorophenyl)-3-methylbutan-2-one (3.9 g, 99%). 1H NMR (400 MHz, CDCl3) δ 7.29 (m, 3H), 7.13 (m, 1H), 1.97 (s, 3H), 1.47 (s, 6H). After stirring 1 h The reaction mixture was partitioned in CH2Cl2 The organic layer was separated washed with 1N HCl and water dried over MgSO4 evaporated in vacuo