First Synthesis of Dodecasubstituted Porphycenes
First Synthesis of Dodecasubstituted Porphycenes
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DOI：
10.1002/chem.201002788
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发表时间：
2011-03-01
影响因子：
4.3
通讯作者：
Uno, Hidemitsu
中科院分区：
文献类型：
--
作者：
Kuzuhara, Daiki;Yamada, Hiroko;Uno, Hidemitsu
十二取代卟啉的合成迄今未见报道。本文首先尝试了通过3，3 ′，4，4 ′-四乙基-5，5 ′-二甲酰基-2，2 ′-联吡咯的McMurry型偶联反应制备四甲基八乙基卟啉，但没有成功地得到十二取代的卟啉，只得到了吡咯并环吩。通过H-1 NMR光谱、FAB MS和X射线晶体结构分析确定了吡咯并环芬的结构。吡咯并环吩没有被成功地氧化成卟啉。在此基础上，首次进行了双环[2.2.2]辛烯（BCOD）稠合5，5 '-二酰基-2，2'-联吡咯的McMurry型偶联反应，成功地合成了四-meso-八-β-取代（十二取代）卟啉。通过核磁共振氢谱和X射线晶体结构分析确定了化合物的结构。与八取代卟啉的晶体结构和NMR谱进行了比较，发现取代基的位置、卟啉内部氮原子的N1-N2和N1-N4距离以及内部NH质子的NMR化学位移之间有很好的相关性，这反映了N1和N2之间N-H中心点中心点N氢键的强度。这些结果表明，BCOD结构相对于普通的烷基是相对紧凑的，这就是为什么十二取代的卟啉是这次可用的。讨论了其紫外/维斯吸收和荧光性质。
The synthesis of dodecasubstituted porphycenes has not been reported, to date. Herein, the preparation of tetramethyloctaethylporphycene by a McMurry-type coupling of 3,3', 4,4'-tetraethyl-5,5'-diformyl-2,2'-bipyrrole was attempted at first, but dodecasubstituted porphycene was not successfully obtained and only pyrrolocyclophene was obtained. The structure of the pyrrolocyclophene was determined by H-1 NMR spectroscopy, FAB MS, and X-ray crystal-structure analysis. The pyrrolocyclophene was not successfully oxidized to porphycene. Then, the McMurry-type coupling of bicyclo[2.2.2]octadiene (BCOD)-fused 5,5'diacyl-2,2'-bipyrroles was performed and tetra-meso-octa-beta-substituted (dodecasubstituted) porphycenes were successfully obtained for the first time. The structures were determined by H-1 NMR spectroscopy and X-ray crystal-structure analysis. The crystal structures and NMR spectra were compared carefully with octasubstituted porphycenes, and there was a good correlation between the position of the substituents, the N1-N2 and N1-N4 distances of the porphycene inner nitrogen atoms, and NMR chemical shifts of the inner NH protons, which expressed the strength of N-H center dot center dot center dot N hydrogen bonding between N1 and N2. These results suggested that the BCOD structure was relatively compact compared with common alkyl groups and that was why the dodecasubstituted porphycenes were available this time. UV/Vis absorption and fluorescence properties are also discussed.