To a stirring solution of 2-aminopyrimidine-5 -carbonitrile (1.0 g, 8.33 mmol) in CH3CN (15 ml) at room temperature under Argon added copper (II) chloride (1.679 g, 12.5 mmol) and test-butyl nitrite (1.288 g, 12.5 mmol). The reaction mixture was placed under Argon in a preheated oil bath (60 ℃). The reaction mixture was cooled to room temperature, and 20 ml of ether was added. The resulting insoluble material was filtered, and the filtrate was concentrated. The crude product was dissolved in a small amount of DCM (~2 ml) and loaded onto a 40 g ISCO silica gel column which was eluted with a 20 min gradient from 0% to 100% EtOAc/Hexanes. 723 mg (61%) of 2-chloropyrimidine-5-carbonitrile was obtained as a tan solid.
