2-Bromo-5-methoxybenzenamine

1-Bromo-4-methoxy-2-nitrobenzene (1.71g, 7.2 mmol, 1 equiv.) was dissolved in EtOH (7 mL) and H2O (5 mL). Iron powder (2.00 g, 35.7 mmol, 5 equiv.) and NH4Cl (1.53 g, 28.6 mmol, 4 equiv.) were added to the solution. The solution was heated to reflux for 2 h. The black organic phase was washed with diethyl ether(4 x 100 mL). This yielded 2-bromo-5-methoxyaniline (95percent) as a green substance, with data as reported.7 At 0 °C a solution of the crude 2-bromo-5-methoxyaniline (1.50 g, 7.4 mmol, 1equiv.) in conc. HCl (7 mL) was treated dropwise with aq. NaNO2 (0.5 g, 7.2 mmol, 1 equiv.)in deionized H2O (5 mL). Stirring was continued at 0 °C for 5 h resulting in the formation ofthe diazonium salt. In a separate flask, at 0 °C, H2O (8 mL) was treated with thionyl chloride(2.2 mL, 30.3 mmol, 4 equiv.). Stirring continued at 0 °C for 1 h. The aqueous phase was washed with ethylacetate (6 x 50 mL). The combined phases were dried over MgSO4. Solvent removal followed by column chromatography (c-Hex-EtOAc; 5:1) yielded S5 (1.50 g, 46percent) asa yellow oil. Rf = 0.3 (c-Hex-EtOAc; 5:1) with data as reported.8Step i :To a 1 L flask equipped with a mechanical stirrer is added 55a (30 g, 129 mmo.) in acetic acid (300 ml_). To this mixture is added iron powder (14.4 g, 258 mmol) slowly in aliquots. The mixture is heated at 50A mixture of 1-bromo-4-methoxy-2-nitro-benzene (10 g, 43 mmol) and Raney Ni (5 g) in ethanol (100 mL) was stirred under HA mixture of 1-bromo-4-methoxy-2-nitro-benzene (10 g, 43 mmol) and Raney Ni (5 g) in ethanol (100 mL) was stirred under HExample I-XIPreparation of Compound 314General Procedure I-CSA mixture of 4-bromo-3-nitroanisole (5 g, 21.6 mmol) and Fe (9.7 g, 0.17 mol) in 30 mL of acetic acid was stirred at r.t for 2 h. After removal of the solvent under reduced pressure, the brown residue was taken up in 100 mL of water and treated with 10percent of aq. KTo a suspension of Zn (3.92 g, 60.3 mmol) in EtOH (80 mL) was added HOAc (3 mL), followed by solution of compound 5-1 (2.0 g, 8.6 mmol) in EtOH (20 mL) at rt. After stirring at rt overnight, the reaction mixture was filtered. The filtrate was concentrated and the residue was diluted with EtOAc (150 mL). The mixture was washed with water (200 mL) and brine (100 mL) and dried with anhydrous Nam-Anisidine (5.00 g, 40.6 mmol) was dissolved in chloroform (40 mL) and the solution was chilled to 5 °C. N-Bromosuccinimide (7.23 g, 40.6 mmol) was added portionwise to the chilled solution over a 1 h period and the mixture was then stirred for another 4 h in an ice bath at 5-10 °C. The reaction mixture was allowed to warm at room temperature and stirring was continued overnight. The mixture was washed with sodium hydroxide (2 M, 50 mL), followed by water (60 mL) and dried over anhydrous sodium sulfate. The solvent was evaporated to afford a dark brown viscous liquid. The crude material was chromatographed (silica gel, dichloromethane/hexane 2:1) to afford a mixture of 2-bromo-5-methoxyaniline and 2, 4-dibromo-5-methoxyaniline as the first major band eluted. Subsequently, another major band was eluted to afford 4-bromo-3-methoxyaniline (860 mg, 10percent) as peach coloured crystals: mp 97-98 °C (lit.(i)

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