三氟乙酸和三氟化硼乙醚在硫杂卟啉合成中的应用  

Application of TFA and BF_3·Et_2O in the Synthesis of Dithiaporphyrins

作　　者：朱岩[1] 朱义州[1] 张经明[1] 郑健禺[1] 

机构地区：[1]南开大学元素有机化学研究所,元素有机化学国家重点实验室,天津300071

出　　处：《高等学校化学学报》2008年第9期1760-1764,共5页Chemical Journal of Chinese Universities

基　　金：国家“九七三”计划(批准号:2006CB932900);国家自然科学基金(批准号:20572048,20421202);天津市科技计划项目基金(批准号:07QTPTJC29700);南开大学亚洲研究中心项目基金(批准号:AS0528)资助

摘　　要：利用三氟乙酸和三氟化硼乙醚在醇羟基与吡咯反应中的催化活性差异,使非对称取代噻吩双醇中的羟基选择性地与吡咯反应,得到单吡咯或双吡咯中间体.这些中间体经进一步的环化反应,得到一系列21,23-二硫杂卟啉衍生物,并通过核磁共振氢谱、质谱、紫外-可见光谱和荧光光谱对其结构进行了表征.Core-modified porphyrins, in which one or more internal nitrogen atoms are replaced with other heteroatoms or carbon, have shown some novel properties such as stabilizing unusual metal oxidation states, catalysis, and photodynamic therapy （PDT）, and nonlinear optical properties. To systematically exploit the distinctive properties of core-modified porphyrins requires the ability to locate not only the heteroatom in the core of the porphyrin but also arrange substituents about the porphyrin perimeter. In this article, an effective process to synthesize dithiaporphyrin derivatives was achieved. The key intermediates with one or two pyrrole groups could be selectively synthesized by treating unsymmetrical thiophene with TFA or BF3 ·Et20, respectively. The structures of these dithiaporphyrins were charcterized by 1H NMR spectra, ESI-MS, HR-MS, IR, UV-Vis spectra and fluorescence spectra.

关 键 词：硫杂卟啉 三氟乙酸 三氟化硼乙醚 催化 

分 类 号：O621[理学—有机化学]