新型meso位芘取代氟硼二吡咯衍生物的合成及光敏活性

Synthesis and Photosensitive Properties of Novel Meso-Pyrenyl-Substituted Boron Dipyrromethene Derivatives

以1-芘甲醛为原料分别与2,4-二甲基吡咯和吡咯进行缩合反应,经由2,3-二氯-5,6-二氰对苯醌氧化脱氢、三氟化硼乙醚络合物配位后得到两种meso位芘取代的氟硼二吡咯(BODIPY)染料1和2。1和2经Vilsmeier-Haack反应引入醛基后分别与2,4-二甲基吡咯和吡咯反应得到四种meso位芘取代的BODIPY二聚体(1a,1b,2a,2b);将染料1通过碘化反应生成单碘代产物1c和二碘代产物1d,其结构经1H NMR,13C NMR和HR-MS(APCI)表征,以1,3-二苯基异苯并呋喃(DPBF)为单线态氧捕获剂测试了各衍生物的光敏氧化性能。结果表明:1a^1d的光敏氧化活性均高于母体1,碘代产物1c的光敏活性提升最大,对DPBF的光敏降解速率可达1的12.0倍,半数降解时间仅为29 s;2的光敏降解速率是1的4.9倍,光照72 s即可实现半数降解。

Two meso-pyrenyl-substituted boron dipyrromethene(Bodipy)dyes,1 and 2,were synthesized via condensation reaction by using 1-pyrenecarboxaldehyde as raw material,followed by oxidative dehydrogenation with 2,3-dichloro-5,6-dicyano-p-benzoquinone and coordination with boron trifluoride ether complex.Aldehyde groups were introduced into dyes 1 and 2 through Vilsmeier-Haack reaction,and the obtained two intermediates were respectively reacted with 2,4-dimethylpyrrole and pyrrole to form four BODIPY dimers with pyrenyl groups at their meso positions(1a,1b,2a,2b).Dye 1 was subjected to an iodination reaction to produce a monoiodo derivative 1c and a diiodo derivative 1d.The structure of each derivative was characterized by 1H NMR,13C NMR and HR-MS(APCI).The photo-oxidative performance of each derivative was tested using 1,3-diphenylisobenzofuran(DPBF)as the singlet oxygen trapping agent.The results show that the photosensitive activities of 1a^1d are enhanced compared to that of precursor 1.The iodinated product 1c has the greatest increase in photosensitive property,whose DPBF photo-oxidative degradation rate is 12.0 times that of 1 and the half-degradation time is only 29 s.The DPBF degradation rate of 2 is 4.9 times that of 1 and the half-degradation time of 2 is 72 s.