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General procedure for the synthesis of 2-amino-4-methyl-5-bromopyrimidine from 2-amino-4-methylpyrimidine: To a solution of 4-methylpyrimidin-2-ylamine (10.9 g, 100 mmol) in chloroform (400 mL) was added N-bromosuccinimide (17.8 g, 100 mmol). The reaction mixture was stirred under light-avoiding conditions for 15 hours. Upon completion of the reaction, the mixture was transferred to dichloromethane (140 mL) and washed sequentially with 1N sodium hydroxide solution (3 x 200 mL) and saturated sodium chloride solution (100 mL). The organic phase was dried with anhydrous sodium sulfate, filtered and concentrated to give 5-bromo-4-methylpyrimidin-2-ylamine (18.8 g, 99% yield). The product was detected by LCMS (m/z): 188.0/190.0 (MH+). 1H NMR (CDCl3) data: δ 8.22 (s, 1H), 5.02 (bs, 2H), 2.44 (s, 3H).

[1] Patent: WO2007/84786, 2007, A1. Location in patent: Page/Page column 91-92
[2] ACS Medicinal Chemistry Letters, 2011, vol. 2, # 10, p. 774 - 779
[3] Patent: WO2011/130628, 2011, A1. Location in patent: Page/Page column 180
[4] Patent: US2013/102595, 2013, A1. Location in patent: Paragraph 0377; 0378
[5] Patent: JP2015/187145, 2015, A. Location in patent: Paragraph 0330