4-bromo-2-N-ethylbenzene-1,2-diamine

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

実験手順: A suspension of (5-bromo-2-nitro-phenyl)-ethyl-amine (Step 26.3) (6 g, 24.48 mmol) and Raney nickel (2 g) in MeOH/THF (1:1 v/v, 600 mL) is stirred for 9 h at rt, under a hydrogen atmosphere. The reaction mixture is filtered through a pad of celite and concentrated. The residue purified by silica gel column chromatography (Hex/EtOAc, 95:5→85:15) to afford 4.51 g of the title compound as a black oil: ESI-MS: 213.1/215.1 [M−H]−; tR=2.53 min (System 1); TLC: Rf=0.57 (Hex/EtOAc, 1:1). The reaction mixture is filtered through a pad of celite concentrated The residue purified by silica gel column chromatography (Hex/EtOAc, 95:5→85:15)

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

実験手順: A suspension of (5-bromo-2-nitro-phenyl)-ethyl-amine (Step 26.3) (6 g, 24.48 mmol) and Raney nickel (2 g) in MeOH/THF (1:1 v/v, 600 mL) is stirred for 9 h at rt, under a hydrogen atmosphere. The reaction mixture is filtered through a pad of celite and concentrated. The residue purified by silica gel column chromatography (Hex/EtOAc, 95:5→85:15) to afford 4.51 g of the title compound as a black oil: ESI-MS: 213.1/215.1 [M−H]−; tR=2.53 min (System 1); TLC: Rf=0.57 (Hex/EtOAc, 1:1). The reaction mixture is filtered through a pad of celite concentrated The residue purified by silica gel column chromatography (Hex/EtOAc, 95:5→85:15)

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

実験手順: A suspension of (5-bromo-2-nitro-phenyl)-ethyl-amine (Step 26.3) (6 g, 24.48 mmol) and Raney nickel (2 g) in MeOH/THF (1:1 v/v, 600 mL) is stirred for 9 h at rt, under a hydrogen atmosphere. The reaction mixture is filtered through a pad of celite and concentrated. The residue purified by silica gel column chromatography (Hex/EtOAc, 95:5→85:15) to afford 4.51 g of the title compound as a black oil: ESI-MS: 213.1/215.1 [M−H]−; tR=2.53 min (System 1); TLC: Rf=0.57 (Hex/EtOAc, 1:1). The reaction mixture is filtered through a pad of celite concentrated The residue purified by silica gel column chromatography (Hex/EtOAc, 95:5→85:15)

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

実験手順: HATU (4.89 g) was added to a solution of 4-bromo-N2-ethylbenzene-1,2-diamine (2.63 g), N,N-diisopropylethylamine (6.40 ml) and cyclopropanecarboxylic acid (0.979 ml) in DMF (40 ml) at room temperature. The mixture was stirred at room temperature for 1 h. The mixture was quenched with water and extracted with EtOAc. The organic layer was separated, washed with water and brine, dried over MgSO4 and concentrated in vacuo. The residue was dissolved into AcOH (40.0 ml), and the mixture was stirred at 80° C. for 1 h. After concentration of the mixture, the residue was neutralized with saturated NaHCO3 solution and extracted with EtOAc. The organic layer was separated, washed with water and brine, dried over MgSO4 and concentrated in vacuo. The residue was purified by silica gel column chromatography (hexane/EtOAc) to give the title compound (1.2 g) as a pale yellow solid. The mixture was quenched with water extracted with EtOAc The organic layer was separated washed with water and brine dried over MgSO4 concentrated in vacuo The residue was dissolved into AcOH (40.0 ml) the mixture was stirred at 80° C. for 1 h extracted with EtOAc The organic layer was separated washed with water and brine dried over MgSO4 concentrated in vacuo The residue was purified by silica gel column chromatography (hexane/EtOAc)

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

実験手順: Zinc (8.0 g) was added to a solution of 5-bromo-N-ethyl-2-nitroaniline (3.0 g) in AcOH (60 ml) at room temperature. The mixture was stirred at room temperature for 30 min. The insoluble material was removed by filtration, and the filtrate was concentrated in vacuo. The mixture was neutralized with saturated NaHCO3 solution at room temperature and extracted with EtOAc. The organic layer was separated, washed with water and brine, dried over MgSO4 and concentrated in vacuo to give the title compound (1.2 g) as a pale yellow solid. The insoluble material was removed by filtration the filtrate was concentrated in vacuo was neutralized with saturated NaHCO3 solution at room temperature extracted with EtOAc The organic layer was separated washed with water and brine dried over MgSO4 concentrated in vacuo

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

実験手順: HATU (4.89 g) was added to a solution of 4-bromo-N2-ethylbenzene-1,2-diamine (2.63 g), N,N-diisopropylethylamine (6.40 ml) and cyclopropanecarboxylic acid (0.979 ml) in DMF (40 ml) at room temperature. The mixture was stirred at room temperature for 1 h. The mixture was quenched with water and extracted with EtOAc. The organic layer was separated, washed with water and brine, dried over MgSO4 and concentrated in vacuo. The residue was dissolved into AcOH (40.0 ml), and the mixture was stirred at 80° C. for 1 h. After concentration of the mixture, the residue was neutralized with saturated NaHCO3 solution and extracted with EtOAc. The organic layer was separated, washed with water and brine, dried over MgSO4 and concentrated in vacuo. The residue was purified by silica gel column chromatography (hexane/EtOAc) to give the title compound (1.2 g) as a pale yellow solid. The mixture was quenched with water extracted with EtOAc The organic layer was separated washed with water and brine dried over MgSO4 concentrated in vacuo The residue was dissolved into AcOH (40.0 ml) the mixture was stirred at 80° C. for 1 h extracted with EtOAc The organic layer was separated washed with water and brine dried over MgSO4 concentrated in vacuo The residue was purified by silica gel column chromatography (hexane/EtOAc)

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

実験手順: A suspension of (5-bromo-2-nitro-phenyl)-ethyl-amine (Step 26.3) (6 g, 24.48 mmol) and Raney nickel (2 g) in MeOH/THF (1:1 v/v, 600 mL) is stirred for 9 h at rt, under a hydrogen atmosphere. The reaction mixture is filtered through a pad of celite and concentrated. The residue purified by silica gel column chromatography (Hex/EtOAc, 95:5→85:15) to afford 4.51 g of the title compound as a black oil: ESI-MS: 213.1/215.1 [M−H]−; tR=2.53 min (System 1); TLC: Rf=0.57 (Hex/EtOAc, 1:1). The reaction mixture is filtered through a pad of celite concentrated The residue purified by silica gel column chromatography (Hex/EtOAc, 95:5→85:15)

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

実験手順: A suspension of (5-bromo-2-nitro-phenyl)-ethyl-amine (Step 52.3) (6 g, 24.48 mmol) and Raney nickel (2 g) in MeOH/THF (1:1 v/v, 600 mL) is stirred for 9 h at rt, under a hydrogen atmosphere. The reaction mixture is filtered through a pad of celite and concentrated. The residue purified by silica gel column chromatography (Hex/EtOAc, 95:5→85:15) to afford 4.51 g of the title compound as a black oil: ESI-MS: 213.1/215.1 [M−H]−; tR=2.53 min (System 1); TLC: Rf=0.57 (Hex/EtOAc, 1:1). The reaction mixture is filtered through a pad of celite concentrated The residue purified by silica gel column chromatography (Hex/EtOAc, 95:5→85:15)

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

実験手順: A suspension of (5-bromo-2-nitro-phenyl)-ethyl-amine (Step 26.3) (6 g, 24.48 mmol) and Raney nickel (2 g) in MeOH/THF (1:1 v/v, 600 mL) is stirred for 9 h at rt, under a hydrogen atmosphere. The reaction mixture is filtered through a pad of celite and concentrated. The residue purified by silica gel column chromatography (Hex/EtOAc, 95:5→85:15) to afford 4.51 g of the title compound as a black oil: ESI-MS: 213.1/215.1 [M−H]−; tR=2.53 min (System 1); TLC: Rf=0.57 (Hex/EtOAc, 1:1). The reaction mixture is filtered through a pad of celite concentrated The residue purified by silica gel column chromatography (Hex/EtOAc, 95:5→85:15)