The general procedure for the synthesis of 2,6-dichlorobenzaldehyde oxime as raw material for 2,6-dichlorobenzylamine was as follows: 2,6-dichlorobenzaldehyde oxime (0.121 g, 1 mmol) was mixed and milled with nano Fe3O4 (0.046 g, 0.2 mmol, particle size about 70 nm) in a porcelain mortar. Subsequently, ZrCl4 (0.233 g, 1 mmol) was added and the mixture continued to be ground at room temperature. The mortar was heated in an oil bath until the temperature of the reaction mixture reached 75-80 °C. After batchwise addition of NaBH3CN (0.314 g, 5 mmol), the reaction mixture was continued to be ground at 75-80 °C for 15 min. After the reaction was completed, H2O (5 mL) was added and stirred for 5 min. The mixture was extracted with EtOAc (2 x 5 mL), the organic phases were combined and dried with anhydrous Na2SO4. Evaporation of the solvent gave a pure 2,6-dichlorobenzylamine liquid in 93% yield (0.1 g, see Table 2, entry 1).
