5-bromo-2-nitro-N-phenyl-aniline

4-Bromo-2-fluoro-nitrobenzene (5.6 g, 20.9 mmol) and aniline (2.5 g, 72.2 mmol) are added to 50 ml. of anhydrous NMP. The reaction is heated to 1 10 °C overnight. After cooling to room temperature and removing the solvent, the compound is purified via column chromatography (silica, cyclohexane/ethyl acetate 9:1 ) and obtained as an orange solid in 92percent yield (5.7 g). H-NMR (400 MHz, CD4-bromo-2-fluoronitrobenzene (1.0 g, 4.3 mmol) and aniline (490 mg, 5.2 mmol) are suspended in 1 -methyl-2-pyrrolidon (2 ml_). The mixture is purged with argon, then heated to 50°C for 15 h. Additional aniline (350 mg, 3.7 mmol) is added to the reaction. The mixture is stirred at 50°C for 15 h. After cooling to room temperature the mixture is diluted with 2 ml. of methanol and 15 ml_ of water. The obtained precipitate is filtered and washed twice with methanol/water-solution (2:1 ). The solid is dried at 60°C under vacuum. The desired product is obtained in 88percent yield (1 .1 g). General procedure: A mixture of 4-bromo-2-fluoro-l -nitrobenzene (1.14 g, 1 eq) and aniline (1 eq) in DMF (30 mL) was heated at 80 C and the reaction progression checked by LC MS. After 18 h the reaction was cooled down to room temperature, diluted with water (50 mL) and extracted with DCM (3 x 50 mL). The organic layers were collected, washed with H20 (2 x 50 mL), brine (1 x 50 mL) and dried (MgSC^). The solvent was removed under reduced pressure and the crude product was used in the next reaction without further purification. 1-497, LC MS [M + 1] + m/z 293.00; 1-498, LC MS [M + 1]+ m/z 323.00To a solution of 126 (7.63 g, 26 mmol) in 90 ml DMF, NaH was added (1.35 g, 33.8 mmol, 60 percent dispersion in oil) at 0C, and the mixture was stirred at 0C for 0.5 h. Mel (3.7 g, 26 mmol) was added and the mixture was stirred at 0C for 2 h. The reaction was quenched by adding a saturated aqueous solution of ammonium chloride and extracted with Et20. The combined organic layers were washed with H20, then with brine, and dried over MgSC>4, filtered, and the filtrate was concentrated. The residue was purified by chromatography on silica gel (hexane:CC :EtOAc, 30: 10: 1) to give (5- bromo-2-nitrophenyl)methyl(phenyl)amine (127) (7.5 g, 93 %), 'H-NMR (DMSO-d5, 400 MHz): 7.83 (d, J = 8.8 Hz, 1H), 7.75 (d, J = 2.0 Hz, 1H), 7.53 (dd, Ji = 8.8 Hz, J2 = 2.0 Hz 1H), 7.20 (dd, Ji = J2 = 8.4 Hz, 2H), 6.87 (d, Ji = J2 = 7.2 1H), 6.76 (d, J = 8Hz, 2H), 3.29 (s, 3H).

Molecular Weight:293.12
XLogP3:4.4
Hydrogen Bond Donor Count:1
Hydrogen Bond Acceptor Count:3
Rotatable Bond Count:2
Exact Mass:291.98474
Monoisotopic Mass:291.98474
Topological Polar Surface Area:57.8
Heavy Atom Count:17
Complexity:264
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes