【作者】 李国成；

【导师】 郭灿城； 阳卫军；

【作者基本信息】 湖南大学 ， 有机化学， 2005， 硕士

【摘要】 水溶性卟啉在医学、分子识别、分析化学、电化学及光化学反应等领域具有广泛的用途。用经典的Adler、Lindsey方法及改进后的郭灿城法,合成水溶性卟啉产率低甚至不能合成,同时由于良好的水溶性给分离提纯带来很大困难,使水溶性卟啉的应用受到很大制约。我们课题组的一个研究方向是功能卟啉分子的合成及应用研究,这需要高纯度的带有活性官能团的水溶性卟啉。本论文对水溶性氨基卟啉及磺酸卟啉的合成、分离提纯进行研究,合成了不对称的硝基卟啉、氨基卟啉、磺酸卟啉及带有活性官能团(-NH2)的磺酸卟啉。具体内容如下: A、将四苯基卟啉及5-(4-氨基苯基)-10,15,20-三苯基卟啉磺化,制备了相应的四(4-磺酸苯基)卟啉、5-(4-氨基苯基)-10,15,20-三(4-磺酸苯基)卟啉。对该磺化反应的条件进行了研究,找到了磺化反应的适宜条件(120℃、反应4小时)。利用磺酸卟啉易溶于强极性溶剂、难溶于弱极性溶剂的特性,在甲醇-丙酮体系中成功地纯化了磺酸卟啉。该提纯方法操作简单,产品纯度高,收率达60%,远高于文献报道的收率,解决了水溶性磺酸卟啉分离提纯困难的难题。B、用改进的Adler方法和还原硝基卟啉等两种方法合成了不对称氨基卟啉。将硝基卟啉还原为相应的氨基卟啉的总产率高于直接用混合醛与吡咯聚合制备不对称氨基卟啉的产率。对文献报道的硝基卟啉还原的方法进行了改进,即在N2保护下进行还原,节约了试剂,缩短了时间,提高了产率。C、用改进的Adler方法制备了不对称硝基卟啉,但产率低。参照卟啉用浓硫酸制取磺酸卟啉的原理,用HNO3将卟啉硝化高产率分别获得单硝基卟啉(60%)和二硝基卟啉(52%),并对溶剂、硝酸的用量等影响反应的条件进行了探讨,发现合成单硝卟啉的最佳条件是:0-5℃下,CHCl3为溶剂,n(HNO3)/n(TPP)=17:1; 制备二硝基卟啉条件是:室温下,CH3COOH为溶剂。四苯基卟啉硝化所得到的二硝基卟啉有两种异构体,n(Cis-位二硝基卟啉):n(Trans-位二硝基卟啉)=3.6:1偏离理论值2:1,从理论上对偏离结果作了合理的解释。D、对所合成卟啉的Uv-Vis及1HNMR数据的差异给予了合理的解释。更多还原

【Abstract】 The water-soluble porphyrins play an important role in medicine, molecule identification, analytical chemistry, electrochemistry and photochemistry. But, They were difficult to be prepared in large scale by loading Adler method, Lindsey method or Guo method because of its low yield, also it was very difficult to be separated from the reaction mixture due to its good water-solubility, which limited their application. Synthesis and application studies of functional porphyrin molecules is one of our academic items in our lab. Highly pure functionalized water-soluble porphyrins have been urgently needed. In this researching, synthesis of water-soluble amino-porphyrins and sulfonato-porphyrins has been investigated along with the suitable method for separation and purification of them from the reaction mixture. Based on our modified synthetic methodology, the asymmetric nitro-porphyrin, amino-porphyrin, sulfonato-porphyrin and amino-sulfonato-porphyrin were synthe-sized shown in detail as follows. A.4-Sulfonato-porphyrin and 5-(4-aminophenyl)-10,15,20-tris(4-sulfonato-phenyl)-porphyrin were synthesized by sulfonation of tetraphenylporpyrin and 5-(4-amino phenyl)-10,15, 20-triphenylporphyrin, respectively. After screening the reaction factors, till now the optimum condition of sulfonation is at 120℃ for 4 hs. Sulfonato-porphyrins are poor soluble in the low polar solution, but good soluble in the strongly polar solutions, based on which, the pure sulfonato-porphyrin was obtained in methonal–acetone system successfully. This purification method is very simply and the products obtained by this method is analytically pure. The over all yield could be up to 60%, which is better than the reported yield in literature(15 %). Combined with the synthetic method and purification method developed in this thesis,we successfully got a good methord for synthesis and separation of sulfonato-porphyrin. B.The asymmetrical amino-porphyrin can be prepared by the modified Adler method or via reduction of nitro-porphyrin. The yield of amino-porphyrin from the reduction of nitro-porphyrin was far higher than that from condensating aldehyde with pyrrole. Therefore, we utilize the reduction of nitro-porphyrin after somewhat modification to prepare asymmetrical amino-porphyrin. When the reaction was carried out in the N2 atmosphere, the yield was improved. Also saved stannic chloride(II) and shortened the reactive time. C.The assymmetrical nitro-porphyrin was synthesized by the Adler method with low yield. We changed to nitration of porphyrin with HNO3. Mononitro-porphyrin (60%) and dinitro-porphyrin (52%) were prepared by this method respectively. A series of conditions focus on the solvent and the loaded dosage of HNO3 which affect the nitration of tetraphenylporphyrin were investigated. The results showed that the optimum condition for synthesis of mononitro-porphyrin was at 0-5℃in CHCl3 with n(HNO3)/n(TPP)=17:1 . For dinitro-porphyrin, the optimum condition was at room temperature in CH3COOH. The dinitro-porphyrin has two kind of isomers prepared from tetraphenylporpyrin via nitration. We found that n(cis-dinitro-porphyrin):n(trans-dinitro-porphyrin) is 3.6:1, which was deviated from the theory valve that the molar ratio of them is 2:1. The reasons for the deviation were interpreted reasonably. D.The differences of the data from Uv-vis and 1HNMR of synthesized porphyrin were explained reasonably.更多还原