Nitric Acid → 1-Fluoro-2,3-dimethoxy-5-nitrobenzene

反応式

[N+:1]([O-:4])([OH:3])=[O:2].[F:5][C:6]1[CH:11]=[CH:10][CH:9]=[C:8]([O:12][CH3:13])[C:7]=1[O:14][CH3:15]>>[F:5][C:6]1[C:7]([O:14][CH3:15])=[C:8]([O:12][CH3:13])[CH:9]=[CH:10][C:11]=1[N+:1]([O-:4])=[O:2].[F:5][C:6]1[CH:11]=[C:10]([N+:1]([O-:3])=[O:2])[CH:9]=[C:8]([O:12][CH3:13])[C:7]=1[O:14][CH3:15]

参加物

反応物 2

HCID 944Nitric Acid

HCID 27589791-Fluoro-2,3-dimethoxybenzene

生成物 2

HCID 153116921-Fluoro-2,3-dimethoxy-5-nitrobenzene収率 49%

HCID 21999488Benzene, 2-fluoro-3,4-dimethoxy-1-nitro-収率 28%

実験手順

To a solution of nitric acid (853 ml, 1.91E+04 mmol) stirred at 0° C. was added dropwise 1-fluoro-2,3-dimethoxybenzene (149 g, 954 mmol). The mixture was stirred at the same temperature for 15 min, and then was allowed to warm up to RT for 15 min. The orange solution was poured into ice and the resultant solid was filtered, washed with water and dried. LCMS showed that the pale yellow solid was the mixture of two products (ratio 1/1.8). The crude material was purified by reverse phase automatic C18 column chromatography (Combiflash RF, 120 g column), eluting with Acetonitrile/Water (0-90%) over 35 min to afford 2-fluoro-3,4-dimethoxy-1-nitrobenzene (53 g, 263 mmol, 28% yield) and 1-fluoro-2,3-dimethoxy-5-nitrobenzene (94 g, 467 mmol, 49% yield) as white solids. LCMS: (M+H)+: 202.1.