两种四氨基锌酞菁异构体的简易合成及其表征

Synthesis and Characterization of Two Positional Isomeric Tetraamino-phthalocyanines Zinc(Ⅱ)

分别从 4 -硝基邻苯二甲酰亚胺和 3-硝基邻苯二甲酸酐出发 ,经过两步反应 ,不经色层分离 ,制得了纯净的 2 ,9,1 6 ,2 3-四氨基锌酞菁和 1 ,8,1 5 ,2 2 -四氨基锌酞菁两种异构体 .对所合成的产物进行了质谱、1 H NMR及紫外可见光谱表征 .结果表明 ,两种异构体在其 DMF溶液中有二聚现象 ,其分子上的氨基不易氧化 .前者分子上的氨基动力学稳定性强 ,后者分子上的氨基热力学稳定性强 ,且后者分子中存在分子内氢键 .

Two pure isomers, 2,9,16,23-tetraamino-phthalocyanine zinc(Ⅱ) and 1,8,15,22-tetraamino-phthalocyanine zinc(Ⅱ), have been prepared in two steps from 4-nitro-o-phenyleneimine and 3-nitro-phthalic anhydride respectively and without using chromatographic fractionation. The synthesized compounds were characterized by using 1H NMR MALDI-TOF MS and solution phase electronic (UV-Vis) spectroscopy. Dipolymers in their DMF solution and stability of their amino-group antioxidation were confirmed by mass spectroscopy. Amino-group kinetic stability in the former isomer molecule and thermodynamic stability and intra molecular hydrogen bond in the latter isomer molecule were concluded through discussing their 1H NMR and UV-Vis spectroscopy.