Porphyrins with Exocyclic Rings. 13.1 Synthesis and Spectroscopic Characterization of Highly Modified Porphyrin Chromophores with Fused Acenaphthylene and Benzothiadiazole Rings
Porphyrins with Exocyclic Rings. 13.1 Synthesis and Spectroscopic Characterization of Highly Modified Porphyrin Chromophores with Fused Acenaphthylene and Benzothiadiazole Rings
复制标题
具有环外环的卟啉。
DOI：
10.1021/jo9815655
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发表时间：
1998
影响因子：
3.6
通讯作者：
J. D. Spence
中科院分区：
文献类型：
--
作者：
T. Lash;P. Chandrasekar;A. Osuma;S. T. Chaney;J. D. Spence
作为稠合芳环对卟啉发色团影响研究的一部分，合成了一系列含稠合苊环或苯并噻二唑环的新型结构卟啉。碱催化1-硝基苊烯或4-硝基苯并噻二唑与异氰乙酸酯的缩合反应得到了较好的产率的稠合吡咯5和28。在乙二醇中用KOH裂解酯部分得到未取代的杂环，随后在乙酸/乙醇中与2当量的乙酰氧基甲基吡咯9缩合产生改性的三吡喃12和31。用TFA处理具有末端叔丁基酯单元的三吡喃，并在二氯甲烷中与3，4-二乙基-2，5-吡咯二甲醛13缩合，用DDQ氧化后得到相应的π-延伸的卟啉14和32。苊卟啉14具有独特的紫外维斯光谱，在660 nm附近有一个相对较强的谱带。强烈的红移现象是...
As part of a survey on the influence of fused aromatic rings on the porphyrin chromophore, a series of novel structures with fused acenaphthylene or benzothiadiazole rings have been synthesized. Base-catalyzed condensation of 1-nitroacenaphthylene or 4-nitrobenzothiadiazole with esters of isocyanoacetic acid afforded good yields of the annelated pyrroles 5 and 28. Cleavage of the ester moieties with KOH in refluxing ethylene glycol gave the unsubstituted heterocycles, and subsequent condensation with 2 equiv of acetoxymethylpyrroles 9 in acetic acid/ethanol produced the modified tripyrranes 12 and 31. Tripyrranes with terminal tert-butyl ester units were treated with TFA and condensed with 3,4-diethyl-2,5-pyrroledicarboxaldehyde 13 in dichloromethane to give, following oxidation with DDQ, the corresponding π-extended porphyrins 14 and 32. Acenaphthoporphyrins 14 showed unique UV−vis spectra with a triply split Soret band region and a relatively strong band near 660 nm. Strongly red-shifted absorptions wer...