硝基芳环和硝基杂芳环中氢的替代亲核取代

Vicarious Nucleophilic Substitution of Hydrogen in Nitro Aromatics and Nitro Heteroaromatics

氢的替代亲核取代反应(VNS)是与硝基芳环的亲电反应、亲核反应不同的一种新反应.将VNS与硝基芳环的亲电反应、亲核反应做比较,阐述了VNS的定义;通过对竞比实验、速控步骤和动力学同位素效应的分析,解释了VNS的反应机理;分别从硝基芳环的结构、亲核试剂的类型和反应条件三方面讨论了影响VNS定位效应的因素;介绍了VNS反应的应用,尤其是VNS胺化反应在军事化学中的实际应用.

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.