[Br:1][C:2]1[CH:7]=[C:6]([CH3:8])[C:5](N)=[C:4]([CH3:10])[CH:3]=1.Cl.N([O-])=O.[Na+].C(=O)(O)[O-].[Na+].[C-]#N.[K+].[Cu][C:25]#[N:26]>O>[Br:1][C:2]1[CH:7]=[C:6]([CH3:8])[C:5]([C:25]#[N:26])=[C:4]([CH3:10])[CH:3]=1A mixture of 4-bromo-2,6-dimethylbenzenamine (20 g, 100 mmol) and conc. HCl (100 mL) in water (100 mL) was sonicated for 5 min and then cooled to 0° C. A solution of sodium nitrite (6.9 g, 100 mmol) in water (25 mL) was added, and the resulting mixture was stirred at 0° C. for 30 min, then neutralized by the addition of solid sodium bicarbonate. The resulting mixture was slowly poured (in portions) into a solution of potassium cyanide (6.5 g, 100 mmol) and copper(I) cyanide (9.0 g, 100 mmol) in water (50 mL). The resulting mixture was heated at 70° C. for 30 min, then cooled to 25° C. and extracted with EtOAc (3×150 mL). The combined extracts were washed with brine, dried over MgSO4, filtered, and concentrated in vacuo to provide 4-bromo-2,6-dimethylbenzonitrile as a brown solid. 1H NMR (300 MHz, DMSO-d6) δ ppm 7.56 (s, 2 H), 2.45 (s, 6 H).
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