Nitrenium ions.Part 5. For Part 4 see ref. 1 Reactions of N,N-dimethyl-p-benzoyloxyaniline-iminium chloride with indoles and indolizines. X-ray structure of unexpected [2-chloro-4-(4-dimethylaminophenyl-ONN-azoxy)phenyl]dimethylamine (azoxy derivative)
作者:Lucedio Greci、Riccardo Castagna、Patricia Carloni、Pierluigi Stipa、Corrado Rizzoli、Lara Righi、Paolo Sgarabotto
DOI:10.1039/b308088a
日期:——
N,N-Dimethyl-p-nitrosoaniline reacts with benzoyl chloride affording a complex salt containing a cation, a hybrid between a nitrenium ion and an iminium ion. The salt reacts with nucleophiles (indoles, indolizines) yielding compounds characterized by a new carbon-nitrogen bond, derived from the nitrenium ion form. According to the type of nucleophile, the reaction, to differing extents, is in competition
N,N-二甲基-对亚硝基苯胺与苯甲酰氯反应,得到包含阳离子的络合盐,该络合物是salt离子和亚胺离子之间的杂化物。该盐与亲核试剂(吲哚,吲哚嗪)反应生成化合物,其特征是衍生自氮离子形式的新的碳-氮键。根据亲核试剂的类型,该反应在不同程度上与电子转移过程竞争,该电子转移过程导致亲核试剂的二聚体和对应于N,N-二甲基-对-亚硝基苯胺的a氧基的形成。在所研究的反应之一中,还分离了氯化的氮氧基衍生物,并通过X射线分析阐明了其结构。