4-Bromo-2-methoxybenzenamine

Black particles

o-Anisidine (470 mg, 3.60 mmol) was dissolved in dichloromethane (8 mL) and cooled to -10 °C. 2, 4, 4, 6-Tetrabromocyclohexadione (1.56 g, 3.60 mmol) was slowly added into the above stirred solution, while the temperature was kept below -5 °C. The reaction was allowed to warm to room temperature and stirring was continued overnight. The reaction mixture was washed with sodium hydroxide (10 mL, 2 M) and then water (15 mL), dried over magnesium sulfate, filtered and evaporated to dryness. The residue was chromatographed (silica gel, dichloromethane) to afford 2, 4-dibromo-6-methoxyaniline (90 mg, 9percent) as a dark brown liquid. General procedure: To a magnetic solution of aromatic compound (1 mmol)in acetonitrile (5 mL), OXBTEATB (0.233 g, 0.5 mmol) wasadded and stirred at room temperature for the appropriatetime (Table 1). The reaction was monitored by TLC (eluent:n-hexane/ethyl acetate: 5/1). The reaction mixture was transferredinto a separatory funnel after filtration of OXBTEABand was extracted with water (15 mL) and dichloromethane(20 mL). The organic layer was dried over anhydrousNa2SO4, and the solvent was concentrated in a rotary evaporator.The crude product was purified by passing it over acolumn of silica gel using a mixture of n-hexane and ethylacetate as the eluent. In order to regenerate the reagent, whitesolid was treated with liquid bromine. All the product structureswere confirmed by comparison of melting point or 1HNMR spectra with ones reported in the literature [29a-29e].To a solution of o-anisidine (15 g) in dry dichloromethane (250 ml) at -10 o-Anisidine (0.18 ml, 20 mg, 1.63 mmol, 1 eq) is dissolved in a mixture of 10 ml of dichloromethane and 4 ml of methanol. Preparation 80; 4-Bromo-2-methoxy-phenylamine; Add dropwise a solution of bromine (0.83 mL, 16.2 mmol) in CH2-methoxyaniline (3 g, 24.36 mmol) in acetonitrile (30 mL) was added N- bromosuccinimide (4.34 g, 24.36 mmol) and the reaction mixture was stirred at 15 deg.C for 15 minutes. To the reaction mixture sodium sulfite solution (40 mL) to quench the reaction, the mixture was extracted with ethyl acetate (50ml); the organic layer was dried over sodium sulfate, and concentrated to give the crude product, which was purified by silica gel column chromatography (petroleum ether: ethyl acetate = 10: 1) to give the title compound (2.7 g, 55percent yield) as a yellow solid.To a solution of 2-methoxy-phenylamine (11.27 mL, 12.31 g, 0.1 mol) in glacial acetic acid (250 mL) maintained at about 10 °C a solution of bromine (5.65 mL, 17.58 g, 0.11 mol) in glacial acetic acid (7 mL) was added over 2 h. A purple precipitate was formed, that was filtered on a Buchner funnel and rinsed with glacial acetic acid and petroleum ether (3 x 100 mL) to afford a whitish solid mixture of 4-bromo-2-methoxy-phenylamine and 4, 5-dibromo-2-methoxy- phenylamine (26.9 g). The mixture was separated by flash chromatography on silica gel (hexane/EtOAc 40/60) and the desired compound was crystallized from fert-butyl methyl ether (18.73 g, 82.9percent).Step 3 4-bromo-2-methoxyaniline 4-bromo-2-methoxyaniline

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