Synthesis of Peripherally Nitrated,Aminated, and Arylaminated Subporphyrins |
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Authors: | Eiji Tsurumaki Prof?Dr Atsuhiro Osuka |
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Institution: | Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo‐ku, Kyoto 606‐8502 (Japan), Fax: (+81)?75‐753‐3970 |
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Abstract: | 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 ? 5 H2O 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 , 4b , 4c , 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. |
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Keywords: | amination boron electrochemistry nitration subporphyrins |
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