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Synthesis of Peripherally Nitrated, Aminated, and Arylaminated Subporphyrins
Author(s) -
Tsurumaki Eiji,
Osuka Atsuhiro
Publication year - 2013
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201300869
Subject(s) - nitration , halogenation , nitro , electrochemistry , chemistry , medicinal chemistry , n bromosuccinimide , molecule , organic chemistry , alkyl , electrode
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(NO 3 ) 2 ⋅ 5 H 2 O in a mixed EtOAc/Ac 2 O 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.