5-BROMO-4-FLUORO-2-METHYLANILINE

light brown solid

The mixture of Iron powder (17.8 g, 318 mmol) and [NH4C1] (5.10 g, 95.4 mmol) in water (100 mL) was refluxed for 30 minutes. To this hot mixture was added 4-bromo-3-fluoro-6-nitrotoluene (18.6 g, 79.5 mmol) slowly and then the reaction mixture was refluxed for 48 hours. The mixture was cooled to room temperature and extracted with EtOAc (3 x 200 mL). The organic solution was washed with [H20] (3 x 300 mL) and brine (300 mL), dried (Na2SO4), and concentrated. The residue was purified by flash chromatography (silica, 20percent EtOAc in hexanes) to give 11.7 g (72percent) of title compound as a pale yellow solid. 'H NMR [(CDC13)] : 300 MHz [5] 6.82 (m, 2H), 3.49 (bs, 2H), 2.11 (s, 3H).The mixture of Iron powder (17.8 g, 318 mmol) and [NH4C1] (5.10 g, 95.4 mmol) in water (100 mL) was refluxed for 30 minutes. To this hot mixture was added 4-bromo-3-fluoro-6-nitrotoluene (18.6 g, 79.5 mmol) slowly and then the reaction mixture was refluxed for 48 hours. The mixture was cooled to room temperature and extracted with EtOAc (3 x 200 mL). The organic solution was washed with [H20] (3 x 300 mL) and brine (300 mL), dried (Na2SO4), and concentrated. The residue was purified by flash chromatography (silica, 20% EtOAc in hexanes) to give 11.7 g (72%) of title compound as a pale yellow solid. 'H NMR [(CDC13)] : 300 MHz [5] 6.82 (m, 2H), 3.49 (bs, 2H), 2.11 (s, 3H).[000892j To a stirred solution of compound 2 (7.2 g, 1 eq) in EtOH: H20 (7:3, 100 mL), Iron powder (8.1 g, 5 eq) and NH4C1 (8.5 g, 5 eq) were added. The resulting reaction mixture was refluxed for 3 h. The progress of the reaction was monitored by TLC. After completion of the reaction, the reaction mixture was filtered through a celite and the filtrate was evaporated under reduced pressure. The residue was diluted with water and extracted with ethyl acetate (3 X 50 mL). Combined organic extracts were washed with brine, dried over anhydrous sodium sulfate and evaporated under reduced pressure to afford the title compound. LCMS (mlz): 205.15 (M + 1).To a suspension [OF 5-BROMO-4-FLUORO-2-METHYLANILINE (11.] 2 g, 54.9 mmol) in concentrated [HCL] (35 mL) was added dropwise a solution of sodium nitrite (4.17 g, 60.4 mmol) in water (20 mL) over 30 minutes at [0C.] To the mixture was added dropwise a solution [OF SNCI2*2H2O] (37.2 g, 165 mmol) in concentrated HCl (45 mL) over 1 hour. After stirring for 2 hours at 0 [C, ] the reaction mixture was basified with 50% NaOH (50 mL). The mixture was further diluted with water (50 mL) and treated with another 50% NaOH (20 mL) and then crushed ice (200 g). The reaction mixture was extracted with ether (3 x 200 mL) and the combined organic phases were washed with brine, dried over [NA2SO4, ] and filtered. The filtrate was acidified by adding an anhydrous solution of [HCL] in ether (2 N in ether, 42 mL, 82.5 mmol). The precipitate was collected and dried under reduced pressure to give 9.92 g [(71 %)] of title compound as a pale yellow [SOLID.'H] NMR (DMSO): 300 MHz [6] 10.18 (bs, 3H), 7.98 (bs, 1H), 7.21 (m, 2H), 2.16 (s, 3H).

Molecular Weight:204.04
XLogP3:2.4
Hydrogen Bond Donor Count:1
Hydrogen Bond Acceptor Count:2
Exact Mass:202.97459
Monoisotopic Mass:202.97459
Topological Polar Surface Area:26
Heavy Atom Count:10
Complexity:120
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes