Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3970.
Chem Asian J. 2013 Dec;8(12):3042-50. doi: 10.1002/asia.201300869. Epub 2013 Aug 26.
2-Nitro-5,10,15-tri(4-tert-butylphenyl)subporphyrin 2 was prepared by the nitration of 5,10,15-tri(4-tert- butylphenyl)subporphyrin 1a with five equivalents of Cu(NO3)2·5H2O in a mixed EtOAc/Ac2O solution and was reduced into 2-amino-5,10,15-tri(4-tert-butylphenyl)subporphyrin 3. Bromination of 5,10,15-triphenylsubporphyrin 1b with 1.5 equivalents of N-bromosuccinimide (NBS) gave 2-bromo-5,10,15-triphenylsubporphyrin, which was converted into various 2-arylamino-5,10,15-triphenylsubporphyrins (4a-4d) and 2-benzamido-5,10,15-triphenylsubporphyrin 5 through Pd-catalyzed cross-coupling reactions. These molecules constitute the first examples of mono-β-substituted subporphyrins. These subporphyrins exhibit significantly perturbed optical and electrochemical properties, which reflect a large influence of the peripherally attached substituents on the electronic networks of subporphyrins.
2-硝基-5,10,15-三(4-叔丁基苯基)次卟啉 2 是由 5,10,15-三(4-叔丁基苯基)次卟啉 1a 与五当量的 Cu(NO3)2·5H2O 在混合 EtOAc/Ac2O 溶液中硝化得到的，并被还原为 2-氨基-5,10,15-三(4-叔丁基苯基)次卟啉 3。5,10,15-三苯基次卟啉 1b 与 1.5 当量的 N-溴代丁二酰亚胺 (NBS) 溴化得到 2-溴-5,10,15-三苯基次卟啉，它被转化为各种 2-芳基氨基-5,10,15-三苯基次卟啉 (4a-4d) 和 2-苯甲酰胺-5,10,15-三苯基次卟啉 5 通过钯催化的交叉偶联反应。这些分子构成了单-β-取代次卟啉的第一个例子。这些次卟啉表现出明显受到干扰的光学和电化学性质，这反映了外围连接的取代基对次卟啉电子网络的巨大影响。
