镍 (II) 5,15-二-对甲苯基-八乙基卟啉的乙烯基 Vilsmeier 甲酰化得到相应的内消旋-(2-甲酰基乙烯基)卟啉,在用三氟乙酸处理后,得到相应的苯并氯衍生物。在铜 (II) 配合物的情况下,路易斯酸如 BF3·Et2O 和 SnCl4 催化环化生成苯并二氯环而没有脱金属。5-p-tolyloctaethylporphyrin 的镍 (II) 和铜 (II) 配合物的类似乙烯基 Vilsmeier 甲酰化导致 5-p-tolyl-10-(2-formylvinyl) 卟啉的选择性形成。这些金属配合物的后续环化反应具有明显不同的区域选择性;镍 (II) 配合物有利于在 5-对甲苯基取代基附近的环化,而铜 (II) 配合物有利于相反位点的环化。将这些合成方法应用于 4,4'-亚联苯基桥连的二卟啉导致合成卟啉-苯并二氯异二聚体和苯并二氯苯同二聚体。稳态流感...
Novel transformations of metal porphyrins, such as nickel, zinc, copper, and silver porphyrins, to magnesium porphyrins are described. The reactions were accomplished by using 4‐methylphenylmagnesium bromide in toluene. The scope of the reactions was wide and various magnesium porphyrins were obtained (see figure). The products, acid‐sensitive magnesium porphyrins, were smoothly converted to free‐base