N([O-])=O.[Na+].S(=O)(=O)(O)O.[Cl:10][C:11]1[CH:17]=[C:16]([CH3:18])[CH:15]=[C:14]([Cl:19])[C:12]=1N.C(=O)([O-])[O-].[Na+].[Na+].[C-:26]#[N:27].[K+]>C(O)(=O)C.O.O.O.O.O.O.O.[Ni](Cl)(Cl)Cl>[Cl:10][C:11]1[CH:17]=[C:16]([CH3:18])[CH:15]=[C:14]([Cl:19])[C:12]=1[C:26]#[N:27]Powdered sodium nitrite (20.8 g, 650 mmol) was added in portions to stirred concentrated sulfuric acid (146 ml) at 5° C. The mixture was stirred 30 minutes at ambient temperature and 30 minutes at 50° C., cooled to 5° C., and treated dropwise with a solution of 2,6-dichloro-4-methylaniline (47.0 g, 267 mmol) in acetic acid (158 ml). The mixture was stirred 3 hours at 15° C., slowly poured into a solution of sodium carbonate (253 g, 2.39 mole), potassium cyanide (93.5 g, 1.44 mole), and nickel (III) chloride hexahydrate (45.4 g, 166 mmol) in water (1.3 L). After gas evolution subsided the mixture was stirred for 1 hour at 35° C., cooled, and extracted with diethyl ether. The combined extracts were washed with water, dried over anhydrous magnesium sulfate, and evaporated under vacuum. The residue was dissolved in dichloromethane and chromatographed on a column of silica gel (300 g) eluted with dichloromethane. After a forerun (600 ml), 1 liter of eluent was collected and evaporated under vacuum. The residue was crystallized from n-hexane (200 ml) to provide 14.8 g 2,6-dichloro-4-methylbenzonitrile. The mother liquor was diluted with diethyl ether and chromatographed on silica gel (500 g) using a preparative high-performance liquid chromatograph to provide 7.3 g of product (total yield: 22.1 g [44%]), m.p. 99°-102° C.
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