methyl 3,5-dibromo-4-chlorobenzoate

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

実験手順: (3,5-Dibromo-4-chlorophenyl)methanol: NaBH4 (1.53 g, 40.65 mmol) was added portionwise to a stirred solution of methyl 3,5-dibromo-4-chlorobenzoate (4.45 g, 13.6 mmol) in MeOH (50 mL) at 0° C. The reaction mixture was then stirred at ambient temperature for 8 h. The volatiles were evaporated and the residue was diluted with CH2Cl2 and washed with brine followed by water. The organic layer was dried (Na2SO4), filtered and concentrated to afford the title compound as an off white solid (3.3 g, 80%): 1H NMR (300 MHz, DMSO-d6) δ 7.71 (s, 2H), 5.49 (bs, 1H), 4.48 (d, J=4.5 Hz, 2H); ESIMS m/z 297.9 ([M]+); IR (thin film) 3460, 747, 534 cm−1. The volatiles were evaporated the residue was diluted with CH2Cl2 washed with brine The organic layer was dried (Na2SO4) filtered concentrated

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

実験手順: Methyl 3,5-dibromo-4-chlorobenzoate: CuCl2 (2.82 g, 21.0 mmol) in MeCN (30 mL) was stirred at 80° C. for 30 min. To this mixture tert-butylnitrite (2.7 mL, 23 mmol) was then added dropwise at same temperature and the mixture was stirred for another 10 min. Methyl 4-amino-3,5-dibromobenzoate (5.0 g, 16 mmol) in MeCN (30 mL) was added dropwise to the reaction mixture and then stirred at 80° C. for 30 min. The reaction mixture was brought to ambient temperature and an aqueous ammonia solution (20 mL) was added to the reaction mixture and extracted with petroleum ether. The organic layer was washed with brine followed by water, dried (Na2SO4), filtered and concentrated to afford the title compound as an off white solid (4.5 g, 84%). 1H NMR (300 MHz, DMSO-d6) δ 8.21 (s, 2H), 3.94 (s, 3H); ESIMS m/z 326 ([M]+); IR (thin film) 1732, 746 cm−1. stirred at 80° C. for 30 min was brought to ambient temperature extracted with petroleum ether The organic layer was washed with brine dried (Na2SO4) filtered concentrated

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

実験手順: Methyl 3,5-dibromo-4-chlorobenzoate: CuCl2 (2.82 g, 21.0 mmol) in MeCN (30 mL) was stirred at 80° C. for 30 min. To this mixture tert-butylnitrite (2.7 mL, 23 mmol) was then added dropwise at same temperature and the mixture was stirred for another 10 min. Methyl 4-amino-3,5-dibromobenzoate (5.0 g, 16 mmol) in MeCN (30 mL) was added dropwise to the reaction mixture and then stirred at 80° C. for 30 min. The reaction mixture was brought to ambient temperature and an aqueous ammonia solution (20 mL) was added to the reaction mixture and extracted with petroleum ether. The organic layer was washed with brine followed by water, dried (Na2SO4), filtered and concentrated to afford the title compound as an off white solid (4.5 g, 84%). 1H NMR (300 MHz, DMSO-d6) δ 8.21 (s, 2H), 3.94 (s, 3H); ESIMS m/z 326 ([M]+); IR (thin film) 1732, 746 cm−1. stirred at 80° C. for 30 min was brought to ambient temperature extracted with petroleum ether The organic layer was washed with brine dried (Na2SO4) filtered concentrated

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

実験手順: NaBH4 (1.53 g, 40.65 mmol) was added portionwise to a stirred solution of methyl 3,5-dibromo-4-chlorobenzoate (4.45 g, 13.6 mmol) in MeOH (50 mL) at 0° C. The reaction mixture was then stirred at ambient temperature for 8 h. The volatiles were evaporated and the residue was diluted with CH2Cl2 and washed with brine followed by water. The organic layer was dried (Na2SO4), filtered and concentrated to afford the title compound as an off white solid (3.3 g, 80%): 1H NMR (300 MHz, DMSO-d6) δ 7.71 (s, 2H), 5.49 (bs, 1H), 4.48 (d, J=4.5 Hz, 2H); ESIMS m/z 297.9 ([M]+); IR (thin film) 3460, 747, 534 cm−1. The volatiles were evaporated the residue was diluted with CH2Cl2 washed with brine The organic layer was dried (Na2SO4) filtered concentrated

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

実験手順: NaBH4 (1.53 g, 40.65 mmol) was added portionwise to a stirred solution of methyl 3,5-dibromo-4-chlorobenzoate (4.45 g, 13.6 mmol) in MeOH (50 mL) at 0° C. The reaction mixture was then stirred at ambient temperature for 8 h. The volatiles were evaporated and the residue was diluted with CH2Cl2 and washed with brine followed by water. The organic layer was dried (Na2SO4), filtered and concentrated to afford the title compound as an off white solid (3.3 g, 80%): 1H NMR (300 MHz, DMSO-d6) δ 7.71 (s, 2H), 5.49 (bs, 1H), 4.48 (d, J=4.5 Hz, 2H); ESIMS m/z 297.9 ([M]+); IR (thin film) 3460, 747, 534 cm−1. The volatiles were evaporated the residue was diluted with CH2Cl2 washed with brine The organic layer was dried (Na2SO4) filtered concentrated

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

実験手順: (3,5-Dibromo-4-chlorophenyl)methanol: NaBH4 (1.53 g, 40.65 mmol) was added portionwise to a stirred solution of methyl 3,5-dibromo-4-chlorobenzoate (4.45 g, 13.6 mmol) in MeOH (50 mL) at 0° C. The reaction mixture was then stirred at ambient temperature for 8 h. The volatiles were evaporated and the residue was diluted with CH2Cl2 and washed with brine followed by water. The organic layer was dried (Na2SO4), filtered and concentrated to afford the title compound as an off white solid (3.3 g, 80%): 1H NMR (300 MHz, DMSO-d6) δ 7.71 (s, 2H), 5.49 (bs, 1H), 4.48 (d, J=4.5 Hz, 2H); ESIMS m/z 297.9 ([M]+); IR (thin film) 3460, 747, 534 cm−1. The volatiles were evaporated the residue was diluted with CH2Cl2 washed with brine The organic layer was dried (Na2SO4) filtered concentrated

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

実験手順: Methyl 3,5-dibromo-4-chlorobenzoate: CuCl2 (2.82 g, 21.0 mmol) in MeCN (30 mL) was stirred at 80° C. for 30 min. To this mixture tert-butylnitrite (2.7 mL, 23 mmol) was then added dropwise at same temperature and the mixture was stirred for another 10 min. Methyl 4-amino-3,5-dibromobenzoate (5.0 g, 16 mmol) in MeCN (30 mL) was added dropwise to the reaction mixture and then stirred at 80° C. for 30 min. The reaction mixture was brought to ambient temperature and an aqueous ammonia solution (20 mL) was added to the reaction mixture and extracted with petroleum ether. The organic layer was washed with brine followed by water, dried (Na2SO4), filtered and concentrated to afford the title compound as an off white solid (4.5 g, 84%). 1H NMR (300 MHz, DMSO-d6) δ 8.21 (s, 2H), 3.94 (s, 3H); ESIMS m/z 326 ([M]+); IR (thin film) 1732, 746 cm−1. stirred at 80° C. for 30 min was brought to ambient temperature extracted with petroleum ether The organic layer was washed with brine dried (Na2SO4) filtered concentrated