8-溴-2H-苯并[B][1,4]噁嗪-3(4H)-酮

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of 8-bromo-4H-benzo[1,4]oxazin-3-one (343 mg, 1.5 mmol) in 10 ml anhydrous dimethylformanide was added sodium hydride (120 mg of a 60% suspension in mineral oil, 3.0 mmol) portionwise at 0° C. The solution was stirred with a magnetic stirrer at 0° C. for 20 minutes, at which time the initial gas evolution ended. Benzyl bromide (0.22 ml, 1.8 mmol) was added in one portion and the reaction mixture was stirred at 0° C. for 30 minutes. The solution was allowed to warm to room temperature and the reaction mixture was partitioned between water (50 ml) and ethyl acetate (50 ml). The aqueous layer was extracted with ethyl acetate (2×25 ml) and the combined organic fractions were washed with water (2×25 ml) and brine (2×25 ml). After drying over MgSO4, the organic fraction was concentrated in vacuo and resulting brown residue was purified by flash chromatography (5%–15% Ethyl acetate/Hexane in 30 minutes) to give 402 mg of 4-benzyl-8-bromo-4H-benzo[1,4]oxazin-3-one as a yellow solid (84%). MS: 318 (M+H)+. the reaction mixture was stirred at 0° C. for 30 minutes to warm to room temperature the reaction mixture was partitioned between water (50 ml) and ethyl acetate (50 ml) The aqueous layer was extracted with ethyl acetate (2×25 ml) the combined organic fractions were washed with water (2×25 ml) and brine (2×25 ml) After drying over MgSO4 the organic fraction was concentrated in vacuo resulting brown residue was purified by flash chromatography (5%–15% Ethyl acetate/Hexane in 30 minutes)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: The title compound was prepared using a procedure analogous to bromo-1a,2,3,7b-tetrahydro-1H-cyclopropa[c]quinoline except that 7-bromo-3,7b-dihydro-1H-cyclopropa[c]quinolin-2(1aH)-one was replaced with 8-bromo-2H-benzo[b][1,4]oxazin-3(4H)-one. LCMS, [M+H]+=214.0. 1H NMR (400 MHz, CDCl3) δ 6.90 (dd, J=7.9, 1.5 Hz, 1H), 6.63 (t, J=7.9 Hz, 1H), 6.53 (dd, J=7.9, 1.5 Hz, 1H), 4.33-4.39 (m, 2H), 3.42-3.48 (m, 2H).

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of 2-amino-6-bromophenol (1 g, 5.32 mmol) in acetonitrile (10 mL) and water (10 mL) was added sodium bicarbonate (1.028 g, 12.23 mmol). The mixture was cooled to 0° C. and chloroacetyl chloride (0.554 mL, 6.91 mmol) was added dropwise. The reaction was refluxed overnight. After cooling to room temperature, the mixture was diluted with EtOAc, washed with water, dried over anhydrous MgSO4, filtered, and concentrated to afford the title compound (1.14 g, 94% yield) as a dark brown solid. 1H NMR (400 MHz, CDCl3) δ 8.22 (br. s, 1H), 7.23 (dd, J=8.0, 1.4 Hz, 1H), 6.86 (t, J=8.0 Hz, 1H), 6.76 (dd, J=7.9, 1.3 Hz, 1H), 4.74 (s, 2H). The reaction was refluxed overnight After cooling to room temperature washed with water dried over anhydrous MgSO4 filtered concentrated

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of 8-bromo-4H-benzo[1,4]oxazin-3-one (343 mg, 1.5 mmol) in 10 ml anhydrous dimethylformanide was added sodium hydride (120 mg of a 60% suspension in mineral oil, 3.0 mmol) portionwise at 0° C. The solution was stirred with a magnetic stirrer at 0° C. for 20 minutes, at which time the initial gas evolution ended. Benzyl bromide (0.22 ml, 1.8 mmol) was added in one portion and the reaction mixture was stirred at 0° C. for 30 minutes. The solution was allowed to warm to room temperature and the reaction mixture was partitioned between water (50 ml) and ethyl acetate (50 ml). The aqueous layer was extracted with ethyl acetate (2×25 ml) and the combined organic fractions were washed with water (2×25 ml) and brine (2×25 ml). After drying over MgSO4, the organic fraction was concentrated in vacuo and resulting brown residue was purified by flash chromatography (5%–15% Ethyl acetate/Hexane in 30 minutes) to give 402 mg of 4-benzyl-8-bromo-4H-benzo[1,4]oxazin-3-one as a yellow solid (84%). MS: 318 (M+H)+. the reaction mixture was stirred at 0° C. for 30 minutes to warm to room temperature the reaction mixture was partitioned between water (50 ml) and ethyl acetate (50 ml) The aqueous layer was extracted with ethyl acetate (2×25 ml) the combined organic fractions were washed with water (2×25 ml) and brine (2×25 ml) After drying over MgSO4 the organic fraction was concentrated in vacuo resulting brown residue was purified by flash chromatography (5%–15% Ethyl acetate/Hexane in 30 minutes)