Vicarious nucleophilic substitution (VNS) of hydrogen is a new type of reaction which is different from the usual electrophilic and nucleophilic reactions of the nitro arenes. By comparing VNS with the electrophilic substitution and nucleophilic substitution of nitro aromatic, the definition of VNS is explained. By the analysis of the competition experiment, the rate-limiting step and the kinetic isotope effect, the possible reaction mechanism of VNS is described. Furthermore, the factors that affect the orientation of VNS are discussed from the aspects of the structure of nitro arenes, the properties of nucleophiles and reaction conditions respectively. The practical application of VNS, especially the VNS amination in military chemistry is introduced.

Key words: vicarious nucleophilic substitution of hydrogen, amination, nitro arene, nitro heteroaromatic, vicarious substitute