苝红620的高效绿色合成及其性能

Efficient Green Synthesis and Properties of Perylene Red

摘要:

以市售1,6,7,12-四氯-3,4,9,10-苝四甲酸二酐（TCPBA）为原料，合成了中间体N,N’-二(2,6-二异丙基)苯基-1,6,7,12-四氯-3,4,9,10-苝四甲酸二酰亚胺（BDIP-TCPBI）和产品N,N’-二(2,6-二异丙基)苯基-1,6,7,12-四苯氧基-3,4,9,10-苝四甲酸二酰亚胺（苝红620），其结构经IR, MS和NMR谱进行了确证。反应中引入催化剂二水乙酸锌，使BDIP-TCPBI的合成时间缩短了一半，纯度提高了23%，其最佳工艺条件为：n（TCPBA）：n（2,6-二异丙基苯胺）：n（二水乙酸锌）：n（丙酸） = 1 : 4 : 0.2 : 107, 120℃反应12 h，产率为88%，纯度为84%；使用简便的洗涤代替柱色谱法使苝红620的纯度提高了10%。该合成工艺高效绿色，具有较高的应用前景。光谱研究表明苝红620的斯托克斯位移值为35 nm，循环伏安法获得苝红620的LUMO和HOMO轨道能级分别为-4.144 eV和-4.470 eV，具有较小的荧光自吸，是一种潜在的电子受体材料。

Abstract:

Intermediate N,N’-bis(2,6-diisopropylphenyl)-1,6,7,12-tetrachloroperylene-3,4,9,10- tetracarboxylic acid diimide (BDIP-TCPBI) and product N,N’-bis(2,6-diisopropylphenyl)- 1,6,7,12-tetraphenoxyperylene-3,4,9,10-tetracarboxylic acid diimide (perylene red) were synthesized from commercially available 1,6,7,12-tetrachloroperylene-3,4,9,10-tetracarboxylic bisanhydride (TCPBA), and their structures were characterized with IR, MS and NMR spectra. The reaction time of BDIP-TCPBI was shortened by half and its purity was increased by 23% in the presence of zinc acetate dihydrate as catalyst. The optimum synthesis conditions of BDIP-TCPBI were determined that the molar ratio of n(TCPBA) : n(2,6-Diisopropylaniline) : n(zinc acetate dihydrate) : n(propionic acid) was 1:4:0.2:107 for 12 h at 120°C, the yield and purity of BDIP-TCPBI were 88% and 84%, respectively. Using a simple washing method instead of column chromatography, the purity of perylene red was increased by 10%. This preparation was efficient, green and valuable in practical application. The spectra study indicated that the stokes shift of perylene red was 35 nm. From the estimation of cyclic voltammetry, the LUMO and HOMO orbital energy levels of perylene red were -4.144 eV and -4.470 eV, respectively. Perylene red was a potential electron acceptor material with a weak fluorescence self-absorption.