4-Chloro-6-Methyl-2-(Methylthio)pyriMidine-5-carbonitrile

89853-27-0

1208170-17-5

General procedure for the synthesis of 4-chloro-6-methyl-2-methylthio-5-cyanopyrimidine from 4-amino-6-methyl-2-methylthio-5-cyanopyrimidine: 4-amino-6-methyl-2-(methylthio)pyrimidine-5-carbonitrile (50 g, 0.278 mol) was added to a solution of acetonitrile (800 mL) containing anhydrous copper(II) chloride (44.7 g, 0.334 mol), tert-butyl nitrite (51.6 mL, 0.500 mol) and MgSO4 (10 mg) in a solution of acetonitrile (800 mL) and the reaction was stirred at 80 °C. After 3 hours of reaction, the mixture was cooled to room temperature and filtered. The filtrate was concentrated and the residue was dissolved in ethyl acetate, washed sequentially with water and brine, dried over MgSO4 and concentrated. The crude product was purified by column chromatography (eluent: petroleum ether/ethyl acetate = 3:1, subsequently adjusted to 3:2) to afford the target product 4-chloro-6-methyl-2-methylthio-5-cyanopyrimidine as a white solid (33 g, 59% yield). Mass spectrum (MS): m/z=200.11 ([M+1]+). 1H NMR (300 MHz, DMSO) δ 2.69 (3H, s, CH3), 2.61 (3H, s, SCH3).