5-Bromo-2-(trifluoromethyl)aniline

To a suspension of 4-bromo-2-nitro- 1 -(trifluoromethyl)benzene (4.0 g, 14.9mmol) in ethanol (23OmL), THF (85mL), and water (4OmL) was added ammonium chloride (1.0 g, 18.8mmol) and ferrous powder (5.06 g, 90mmol). The resulting mixture was heated at 80 5-bromo-2-(trifluoromethyl)aniline (1) : To a solution of 4-bromo-2-nitro-l- (trifluoromethyl)benzene (2.0 g, 7.4 mmol) in acetic acid (10.0 mL), Iron powder (1.2 g, 21.8 mmol) was added at 0 °C. The resulting reaction mixture was stirred at room temperature for 2 h. After completion of reaction, the reaction mixture was concentrated under reduced pressure. The residue obtained was diluted with water, basified with saturated sodium bicarbonate solution and extracted with ethyl acetate (2x50 mL). The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to afford 1 (1.4 g, 79percent) as a brown gummy solid. 1H NMR (400 MHz, DMSO-dIn the preparation method of the trifluoromethyl aromatic amine of the present embodiment, the aromatic amine is m-bromoaniline, and the other reactions and post-treatment processes are the same as those in Example 28, and three kinds of trifluoromethyl aromatic amine products are obtained. Under nitrogen or argon atmosphere, 3-bromoaniline 0.4 mmol, 0. 2 mm ' Ir (ppy) (2 mg) And DMF (1 ml) were added to the reaction flask and then irradiated with a blue LED band (7W) at room temperature until complete conversion of the trivalent iodine reagent was completed. 10 ml of a saturated aqueous Na2C03 solution was added thereto, and the mixture was extracted three times with ethyl acetate. The organic layer was washed once with saturated brine, and the organic layer was dried over anhydrous Na2S04. Column chromatography (eluent: petroleum ether 60-90: ethyl acetate = 20: 1-10: 1) to afford the product NIH2Yield 27percent; CF3 • Br ^ A ^ NH2CF, yield 23percent.Pd(dppf)Cl2 (613 mg, 0.84 mmol) was added to a mixture of 5-bromo-2- (trifluoromethyl)aniline (Int 25a) (2.00 g, 8.37 mmol), cyclopropylboronic acid (929 mg, 12.56 mmol) and Na2CO3(1.77 g, 16.70 mmol) in dioxane (25 mL) and the mixture was stirred at 90 C overnight. The mixture was concentrated to dryness and the residue was purified by column chromatography (0-2% EtOAc in PE) to give the title compound as yellow oil.Pd(dppf)Cl2 (613 mg, 0.84 mmol) was added to a mixture of 5-bromo-2- (trifluoromethyl)aniline (Int 23a) (2.00 g, 8.37 mmol), cyclopropylboronic acid (929 mg, 12.56 mmol) and Na2CC>3 (1 .77 g, 16.70 mmol) in dioxane (25 mL) and the mixture was stirred at 90 C overnight. The mixture was concentrated to dryness and the residue was purified by column chromatography (0-2% EtOAc in PE) to give the title compound as yellow oil.A mixture of 5-Bromo-2-trifluoromethyl-phenylamine (1151 mg; 4.80 mmol), 4, 4, 5, 5, 4?, 4?, 5?, 5?-Octamethyl-[2, 2'jbi[[ 1, 3 , 2jdioxaborolanylj (1339 mg; 5.27 mmol), and potassium acetate (941mg; 9.59 mmol) in dioxane (15 ml) was degassed, and then added tetrakis(triphenylphosphine)palladium(0). The reaction mixture was stirred at 100C for 18 hrs.The completed reaction was filtered. The filtrate was concentrated. The crude was purified byBiotage silica gel column (100 g, eluting with EA in hexane 0-30%) to yield the title compound(966 mg, yield 70%). LC-MS (M+1) =288.

Molecular Weight:240.02
XLogP3:2.8
Hydrogen Bond Donor Count:1
Hydrogen Bond Acceptor Count:4
Exact Mass:238.95575
Monoisotopic Mass:238.95575
Topological Polar Surface Area:26
Heavy Atom Count:12
Complexity:159
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes