Selective one-pot synthesis of aminopolyhalobenzonitriles from polyhalobenzotrichlorides in anhydrous ammonia

•Polyhalogenbenzotrichlorides react with NH3 to form aminopolyhalogenbenzonitriles.•One-pot ammonolysis+aminodefluorination occur in the range from −33 to 5°C.•Temperature of introducing the second amino group is higher by 60–100°C.•Efficient method to prepare high-purity mono- and diaminobenzonitriles was developed.