2-BROMO-3-AMINOANISOLE

Step 1.Iron powder (1.08 mol) and ammonium chloride (862 mmol) were added to a solution of the bromide (216 mmol) in ethanol (200 mL) and water (140 mL) and the reaction mixture was heated at reflux for 1 h. To a suspension of 2-bromo-1-methoxy-3-nitrobenzene (3.90 g, 16.81 mmol) and iron powder (2.82 g, 50.4 mmol) in EtOH (50 mL) was added concentrated HC1 (3.08 mL, 37.0 mmol). The mixture was heated at 85 °C for 2.0 h. HPLC indicated a completion of the reaction. After cooled to room temperature, the solvent was removed under vacuum. The residue was suspended in EtOAc and saturated sodium bicarbonate.The insoluble material was removed by filtration through a pad of wet celite. The organic layer of the filtrate was collected, washed with brine, dried over sodium sulfate. After evaporation of solvent, Intermediate iSA (3.25 g, 16.09 mmol, 96 percentyield) was obtained as brown oil. It was used for the next step without further purification. ‘H NMR (500MHz, chloroform-d) 7.08 (t, J=8.1 Hz, 1H), 6.45 (dd, J8.0, 1.4 Hz, 1H), 6.34 (dd, J=8.3, 1.1 Hz, 1H), 3.89 (s, 2H); LC-MS: method A, RT = 1.21 mm, MS (ESI) m/z: 202.0 and 204.0 (M+H)2-bromo-1-methoxy-3-nitrobenzene (1 g, 4.31 mmol), Fe (1.68 g, 30.17 mmol) and NH4Cl (1.61 g, 30.17 mmol)were dissolved in THF (4 mL)/MeOH (4 mL)/H2O (2 mL) solution and stirred for 1 hour under reflux. After terminationof the reaction, the reaction solution was cooled to room temperature, diluted with saturated NaHCO3 solution andextracted with EtOAc. The extract solution was concentrated under reduced pressure and purified by column chromatography(eluent, EtOAc/Hex = 1/5) to obtain the title compound (0.83 g, 95 percent yield).1H NMR (500 MHz, CDCl3) δ 7.05(dd, 1H), 6.42(d, 1H), 6.31(d, 1H), 3.86(s, 3H)2-Bromo-3-nitroanisole B3 (1.00 g; 4.31 MMOL) was dissolved in glacial acetic acid (11.0 mL) and ethanol (11.0 mL). To this solution was added iron powder (0.98 g; 17.5 MMOL). The mixture was stirred at reflux for 3.5 h and worked up. The reaction mixture was diluted with water (35 mL), neutralized with solid Na2CO3 and the product extracted with CH2CI2 (3X 50 mL). The extracts were dried (NA2SO4), filtered and CONCENTRATED IN VACUO to afford the crude product, 2-bromo-3 methoxyaniline B4 (91 percent; 0. 79 g) as a pale yellow oil. MS 201.8 (MH) + ; Homogeneity by HPLC (TFA) 220 nm: 95percent.Step C:; 2-Bromo-3-nitroanisole 1b3 (1.00 g; 4.31 mmol) was dissolved in glacialacetic acid (11.0 mL)/ethanol (11.0 mL) and to the solution was added iron powder(0.98 g; 17.5 mmol). The mixture was stirred at reflux for 3.5 hr and worked up. Thereaction mixture was diluted with water (35 mL), neutralized with solid Na2-Bromo-3-nitroanisole 1b3 (1.00 g; 4.31 mmol) was dissolved in glacial acetic acid (11.0 mL)/ethanol (11.0 mL) and to the solution was added iron powder (0.98 g; 17.5 mmol). 2-Bromo-3-nitroanisole 2b3 (1.00 g; 4.31 mmol) was dissolved in glacialacetic acid (11.0 mL )/ethanol (11.0 mL) and to the solution was added iron powder(0.98 g; 17.5 mmol). The mixture was stirred at reflux for 3.5 hr and worked up. Thereaction mixture was diluted with water (35 mL), neutralized with solid NaStep C; 2-Bromo-3-nitroanisole 2B3 (1.00 g; 4.31 mmol) was dissolved in glacial acetic acid (11.0 mL)/ethanol (11.0 mL) and to the solution was added iron powder (0.98 g; 17.5 mmol). The mixture was stirred at reflux for 3.5 h and worked up. The reaction mixture was diluted with water (35 mL), neutralized with solid NaA solution of 2-bromo-l-methoxy-3 -nitrobenzene (500 mg, 2.16 mmol) in CH

Molecular Weight:202.05
XLogP3:1.9
Hydrogen Bond Donor Count:1
Hydrogen Bond Acceptor Count:2
Rotatable Bond Count:1
Exact Mass:200.97893
Monoisotopic Mass:200.97893
Topological Polar Surface Area:35.2
Heavy Atom Count:10
Complexity:110
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes