苝红620的高效绿色合成及其性能

Efficient Green Synthesis and Properties of Perylene Red

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进行了确证。结果显示：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（HPLC,下同）较文献纯度（68%）高出16%,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的纯度较文献纯度（82%）高出9%。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和–4.470 e V,且具有较小的荧光自吸效应,是一种潜在的电子受体材料。

Intermediate N,N＇bis（2,6-diisopropylpheny）-1,6,7,12-tetrachloroperylen-3,4,9,10-tetracarboxylic acid diimide （BDIP-TCPBI） and product N,N＇bis（2,6-diisopropylphenyl）-1,6,7,12-tetraphcnoxyperylene-3,4,9,10- tetracarboxylic acid diimide （perylene red） were synthesized from commercially available 1,6,7,12- tetrachloroperylene-3,4,9,10-tetracarboxylic dianhydride （TCPBA）, and their structures were characterized by IR, MS and NMR spectra. The introduction of catalyst zinc acetate dihydrate in the reaction reduced the synthesis time of BDIP-TCPBI by half, and the purity （HPLC, the same below） was 16% higher than the purity of the reference （68%）. The optimum synthesis conditions of BDIP- TCPBI were determined that the molar ratio of TCPBA/2,6-diisopropylaniline/zinc acetate dihydrate/propionic acid was 1 ： 4 ： 0.2 ： 107, the reaction time was 12 h, and the reaction temperature was 120℃. Under these conditions, the yield and purity of BDIP-TCPBI were 88% and 84%, respectively. The purity of perylene red was 9% higher than the purity of the reference（82%） by a simple washing method instead of column chromatography. This method for the synthesis of perylene red was efficient, green and valuable in practical application. The spectra study indicated that the stokes shift of perylene red was 35 nm. By using cyclic voltammetry, the LUMO and HOMO orbital energy levels of perylene red were -4.144 eV and -4.470 eV, respectively. In addition, perylene red had a weak fluorescence self-absorption. So it is a potential electron acceptor material.