Application
2,4-Dichloroaniline is an important dye and pharmaceutical intermediate, widely used in fine chemical industries such as pesticides, pharmaceuticals, dyes, and photosensitive materials.
Synthesis
Benzaldehyde oxime (CAS: 56843-28-8, 0.121 g, 1 mmol) was used as a starting material, mixed with nano Fe3O4 (0.046 g, 0.2 mmol, average particle size of about 70 nm) in a porcelain mortar and pestle and ground. Subsequently, ZrCl4 (0.233 g, 1 mmol) was added and the mixture was continued to be ground to homogeneity at room temperature. The mortar was heated in an oil bath to raise the temperature of the reaction mixture to 75-80°C. At this temperature, NaBH3CN (0.314 g, 5 mmol) was added in batches and the reaction mixture was continuously ground for 15 minutes. Upon completion of the reaction, the reaction was quenched by the addition of H2O (5 mL) and stirred for 5 min. The reaction mixture was extracted with EtOAc (2 x 5 mL), the organic phases were combined and dried with anhydrous Na2SO4. The solvent was removed by concentration under reduced pressure to give the pure 2,4-dichlorobenzenemethanamine liquid product in 93% yield (0.1 g, see Table 2, entry 1).
References
[1] Journal of the Chinese Chemical Society, 2005, vol. 52, # 1, p. 109 - 112
[2] Bulletin of the Korean Chemical Society, 2011, vol. 32, # 9, p. 3323 - 3326
[3] Bulletin of the Korean Chemical Society, 2011, vol. 32, # 9, p. 3448 - 3452
[4] Journal of the Iranian Chemical Society, 2015, vol. 12, # 5, p. 873 - 878
[5] Journal of Medicinal Chemistry, 1984, vol. 27, # 9, p. 1111 - 1118
