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在以前的研究工作中我们已经证明芳胺可以有效地光敏化多氯甲烷对双环[2,2,1]-2,5-庚二烯的加成反应。该反应具有百分之百的区域选择性,在我们所选择的实验体系中只得到了3.5-加成物,而没有2.3-加成物。这一结果不同于典型的热诱导自由基加成反应。Latowski等人曾对包含有N-取代芳胺-多氯甲烷体系的光物理和光化学行为进行过详细的研究。指出多氯甲烷有效地猝灭电子给体芳胺化合物的荧光,而这一过程是与二者之间经由基态复合物或激基复合物的电子转移过程相关。根据产物的结构及芳胺-多氯甲烷体系的光物理行为,我们给出了N,N,N′,N′-四甲基联苯二胺(I)(NTMB)光敏化多氯甲烷对双环[2.2.1]-2.5-庚二烯(NBD)的加成反应机理。在该反应机理中包含有离子自由基对[ArNR_2~+CH_(4-x)Cl_x~-]和两性离子自由基复合物(Ⅱ).
We have demonstrated in previous work that aryl amines can effectively photosensitize the addition of methylene chloride to bicyclo [2,2,1] -2,5-heptadiene. The reaction has a one hundred percent regioselectivity with only 3.5-adduct obtained in the experimental system of our choice without the 2.3-adduct. This result is different from the typical heat-induced radical addition reaction. Latowski et al. Have conducted a detailed study of the photophysical and photochemical behavior of N-substituted arylamine-containing polychlorinated methane systems. It is pointed out that polychlorinated methane effectively quenches the fluorescence of the electron donor aromatic amine compound, and this process is related to the electron transfer process between them through the ground state complex or exciplex. According to the structure of the product and the photophysical behavior of the aromatic amine-polychloromethane system, we give the results of photo-polymerisation of N, N, N ’, N’-tetramethylbiphenylenediamine (I) Addition reaction mechanism of bicyclo [2.2.1] -2.5-heptadiene (NBD). The reaction mechanism includes ion radical pair [ArNR_2 ~ + CH_ (4-x) Cl_x ~ -] and zwitterionic radical complex (Ⅱ).