5-bromo-2-nitrobenzenamine

7V-(2-Amino-5-(lH-pyrrol-2-yl)phenyl)-4-methoxybenzamide (147); Scheme 14;;Example 14a; ;13.53 g of 2, 4-dibromonitrobenzene (2) dissolved in 20 mL of DMSO is put in a steal autoclave. 51 mL of an aqueous ammonium hydroxide solution (32 percent) is added, the autoclave is equipped with a magnetic stir bar, sealed and heated to 100 °C for 20 hours. After cooling to room temperature the reaction mixture is given into water, the precipitate is sucked off, washed several times with water and recrystallised from a mixture of DIPE/MeOH (1:1) to give 9.87 g (45.5 mmol) of the desired product as orange crystals (94 percent). Melting point: 148-150 °C. In a sealed reaction tube, add cautiously 6 [ML] of an aqueous solution of ammonia [(32percent)] to a solution of 2, 4-dibromonitrobenzene (1, 6 g) in 2 [ML] of DMSO. Stir for 18 hours at [100°C] and cool to room temperature. Pour the heterogeneous mixture into water and filter the title compound (1.1 [G, , 92percent)] as a yellow solid.5-Bromo-2-nitro aniline To a solution of 4-bromo-2-fluoro-1-nitrobenzene (5 g, 22.7 mmol) in MeOH (5 mL), maintained at 0°C in a sealed tube, was added methanolic ammonia (15 mL). The reaction mixture was stirred at room temperature for 12 h, then concentrated. The crude residue was triturated with pentane and Et20 to afford the title compound (4.5 g, 91percent), which was used for the next step without any further purification. H (400 MHz, CD3OD) 7.93 (d, J9.1 Hz, 1H), 7.18 (d, J2.1 Hz, 1H), 6.74 (dd, J9.2, 2.1 Hz, 1H).Step 1. 5-BromO-2-nitro-phenylamine (2); [0176] To a solution of potassium tert-butoxide (14.5 g; 129.2 MMOL) and copper (L) chloride (301 mg ; 3.04 MMOL) in ETHYLENEGLYCOL DIMETHYLETHER (120 mL), stirred at 0°C under nitrogen, a solution of 1-bromo-4-nitro-benzene (1, 6. 141 g; 30.4 MMOL) and 0-methyl-hydroxylamine hydrochloride (3.174 g; 38 MMOL) in N, NDIMETHYLFORMAMIDE (65 mL) was added drop wise over 103 min, the cooling bath was removed and the mixture was allowed to react at room temperature for 3h, diluted with ethyl acetate (600 mL) and washed with saturated aqueous ammonium chloride. The organic layer was dried (MGS04), filtered and concentrated. After purification by flash chromatography (eluent 25percent ethyl acetate in hexane), 4.96 g (75percent yield) of compound 2 were obtained. [0177] H NMR: (400.2 MHz, CDCI3) 8 (ppm): 7.98 (d, J=9.24, 1H); 7.02 (d, J=1. 98, 1H) ; 6.82 (dd, J=1.98 and 9.24, 1H); 6.12 (bs, 2H).

Molecular Weight:217.02
XLogP3:1.9
Hydrogen Bond Donor Count:1
Hydrogen Bond Acceptor Count:3
Exact Mass:215.95344
Monoisotopic Mass:215.95344
Topological Polar Surface Area:71.8
Heavy Atom Count:11
Complexity:159
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes