1-Bromo-2-methoxy-4-nitrobenzene

light brown crystalline powder

General procedure: Catalytic amounts of copper bromide (1 mol percent) were added to a solution of aniline (2.5 mmol) in acetonitrile (30 ml), camphorsulfonic acid (3.0 mmol), sodium nitrite or tert-butyl nitrite (3.0 mmol), and tetrabutylammonium bromide (5.0 mmol). The reaction mixture was stirred at 60 °C for 24 h (Tables 1 and 2). The evolution of NH2SO4 (1.5 mL) was added slowly to a cold (0°C) stirred mixture of 2-methoxy-4-nitrobenzenamine (340 mg. 2.02 mmol) and NaNO2 (186 mg, 2.69 mmol) in H2O (4.0 mL). After the addition was completed, stirring was continued for an additional 30 min at 0°C. Then a solution of CuBr (345 mg, 2.40 mmol) in HBr (1.5 mL) was added slowly at 0°C. The whole was stirred at r.t. overnight and diluted with CHCl3. The organic layer was washed with water and brine, dried and concentrated. Column chromatography (n-hexane : AcOEt=3 : 1) gave the title compound (358 mg, 1.62 mmol, 80percent) as a white solid. 1H-NMR (500 MHz, CDCl3) δ: 7.72–7.67 (3H, m), 3.97 (3H, s).To a solution of 2-bromo-5-nitrophenol (20 g, 92.2 mmol) in THF (300 mL) cooled to 0 °C was added lithium hydroxide (3.87 g, 92.2 mmol) and the mixture wasstirred for 1 h. To this mixture dimethylsulfate (17.5 mL, 184.4 mmol) was added dropwise and the mixture was warmed to room temperature. Stirring was continued overnight. Upon completion of the reaction, the mixture was quenched by the addition of water (200 mL) and extracted using ethyl acetate (3 x 200 mL). The combined organic layers were washed with brine solution (100 mL), dried oversodium sulfate and concentrated under reduced pressure to afford 1 -bromo-2-methoxy-4-nitrobenzene (23.0 g, quantitative yield) as a pale yellow solid: GC-MS(El) m/e 230.9 [(M), calcd for C7H6BrNO3, 230.9]; GC/MS retention time (methodA): tp. = 7.61 mm (GC-MS was performed using Agilent GCMS Module-7890 (GC)5975C(MSD) fitted with column - HP-5M5, 30m x 0.25mm ID x 0.25um Film thickness with helium flow of 0.9 mL/min. Column gradient 50 °C for 1 mm and raised to 300 °C at the rate of 25 °C/min).

Molecular Weight:232.03
XLogP3:2.8
Hydrogen Bond Acceptor Count:3
Rotatable Bond Count:1
Exact Mass:230.95311
Monoisotopic Mass:230.95311
Topological Polar Surface Area:55
Heavy Atom Count:12
Complexity:171
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes