Development of New Reactions Using Charge Transfer Complex Based on New Concept

本论文基于在特定溶剂中形成自由基离子对的新概念，对电荷转移络合物如π-给体- π-受体体系和π-给体- σ-受体体系等新反应的发展进行了研究，取得了如下显著成果：1）发现了芳香族腙（π-给体）与四氰基乙烯反应生成烯烃和杂原子的亚胺复分解新反应（π-受体）在作为特定溶剂的乙腈中的反应。2）制备4，4 '-亚甲基双的新反应（N，N-dimethylaniline）（major）4，4'，4”-methylidyne-tris（N，N-二甲基苯胺）（微量）和痕量的N-[4-[双[4-（二甲氨基）-苯基]亚甲基]-2，5-环己二烯-1-亚基]-N-甲基甲胺溴化物是通过N，N-二甲基苯胺与四卤代甲烷如四溴甲烷和四氯甲烷的乙腈溶液。该反应被认为是由N，N-二甲基苯胺（π-供体）向四卤甲烷（σ-受体）的电子转移引发的。

This study was investigated on the development of new reactions using charge transfer complex such as π-donor - π-acceptor system and π-donor - σ-acceptor system based on new concept as formation of radical ion pair dyad in specific solvation.The results were noticeable such as showing below.1) New imine metathesis obtaied olefin and hetero atom was found by the reaction of aromatic hydrazones (π-donor) with tetracyanoethylene (π-acceptor) in asetonitrile as specific solvent.2) Novel reaction producing 4,4'-methylenebis(N,N-dimetylaniline) (major) 4,4', 4"-metylidyne-tris(N,N-dimethylaniline) (minor) and trace amount of N-[4[bis[4-(dimethylamino)-phenyl]methylene]-2,5-cyclohexadien-1-ylidene]-N- methylmethanaminum bromide was found by the reaction of N,N-dimetylanilines with tetrahalomethanes such as tetrabromomethane and tetrachlolomethane in acetonitrile. The reaction is cosidered to be initiated by the electron transfer from N,N-dimethylaniline (π-donor) to tetrahalomethane (σ-acceptor).