[H-].[Na+].[C:3]([O:11][CH2:12]C)(=[O:10])[CH2:4][C:5]([O:7][CH2:8]C)=[O:6].[Cl:14][C:15]1[CH:16]=[C:17]([CH:20]=[CH:21][C:22]=1Br)[C:18]#[N:19].Cl>O1CCOCC1.[Cu]Br.O>[CH3:8][O:7][C:5](=[O:6])[CH:4]([C:22]1[CH:21]=[CH:20][C:17]([C:18]#[N:19])=[CH:16][C:15]=1[Cl:14])[C:3]([O:11][CH3:12])=[O:10]
7.6 g (0.191 mol) of 60% strength sodium hydride in paraffin oil were initially charged in 300 ml of dioxane. At from 55° C. to 60° C., 22.9 g (0.173 mol) of diethyl malonate were added dropwise, and the mixture was stirred at 50° C. for 1-2 hours. 9.9-g (0.069 mol) of copper(1) bromide were added. At 80° C., 15 g (0.069 mol) of 3-chloro-4-bromobenzonitrile were then added dropwise, and the mixture was subsequently stirred at 100° C. for 14 hours. The reaction mixture was then cooled and acidified by dropwise addition of concentrated hydrochloric acid at from 15° C. to 20° C. Water was added, the mixture was extracted with dichloromethane, the organic phase was dried over sodium sulphate and the solvent was removed. The residue was distilled at 1 mbar, giving 17.5 g of dimethyl(2-chloro-4-cyanophenyl)malonate.
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