【作者】 王立功；

【导师】 郭灿城；

【作者基本信息】 湖南大学 ， 有机化学， 2008， 硕士

【摘要】 本文以卟啉化合物的合成方法及其发光性能研究为目的,设计并合成了两种β-吡咯位取代含氮多芳氨基卟啉:2-(4-N,N-二苯基)苯基-3,7,8,17,18-五甲基卟啉(TPAPMP)和β-3,8,13,18-四甲基-2,7,12,17-四(4-N,N-二苯基)苯基卟啉(TMTTPAP),对合成卟啉分子的光谱性能进行了分析研究。3,4-二取代吡咯是合成β-吡咯位取代卟啉重要中间体,对其合成方法Barton-Zard法进行了一定的研究。本论文具体内容由以下几部分组成:1.简单地介绍了3,4-二取代吡咯和β-吡咯位取代卟啉的研究现状,对Barton-Zard反应的研究进展作了重点的阐述。2.利用Barton-Zard吡咯合成法合成了六个未见报道的代表性的3,4-二取代吡咯化合物——3-(4-N,N-二苯基)苯基-4-甲基吡咯-2-甲酸酯和5个烷基-8-对甲苯磺酰氧基-喹啉并[5,6,c]吡咯-2-甲酸酯。3.改进了Barton-Zard反应条件,即以易得的无机碱碳酸钾代替容易水解的有机碱1,8-二氮杂双环[5,4,0]-7-十一烯(DBU)和叔丁醇钾,改进后的方法可用于文中所有3,4-二取代吡咯的合成,具有适应性广、便于操作的特点。4.以3-(4-N,N-二苯基)苯基-4-甲基吡咯-2-甲酸酯为中间体,通过单吡咯自聚法合成了具有对称结构的β-3,8,13,18-四甲基-2,7,12,17-四(4-N,N-二苯基)苯基卟啉;以3-(4-N,N-二苯基)苯基-4-甲基吡咯为中间体,通过“3+1”法合成了不对称的2-(4-N,N-二苯基)苯基-3,7,8,17,18-五甲基卟啉。所合成卟啉都未见文献报道。5.研究了2-(4-N,N-二苯基)苯基-3,7,8,17,18-五甲基卟啉和β-3,8,13,18-四甲基-2,7,12,17-四(4-N,N-二苯基)苯基卟啉的光谱性能,并进一步研究了化合物结构的改变对光谱性能的影响。更多还原

【Abstract】 The aim of this thesis was to study on the synthetic methodology and spectral properties of porphyrins, so we synthesized two kinds ofβ-pyrrolic substituted porphyrins: 2-(4-N,N-diphenyl)phenyl-3,7,8,17,18-pentamethylporphyrin andβ-3,8,13,18-tetramethyl- 2,7,12,17-tetra(4-N,N-diphenyl)phenylporphyrin. The spectral properties of those porphyrins were resarched. 3,4-disubstituted pyrrole is an important intermediate ofβ-pyrrolic substituted porphyrins.We researched their synthetic methodology,Barton-Zard reaction. The main contents of this thesis are as follows:1. The synthetic methodology of 3,4-disubstituted pyrrole andβ-pyrrolic substituted porphyrin was briefly introduced and the development of the Barton-Zard reaction was sressed.2. Six representative new 3,4-disubstituted pyrroles, ethyl-3-(4-N,N-diphenyl)phenyl -4-methyl-pyrrole-2-carboxylate and alkyl-8-tosyl-quinolino[5,6,c]pyrrole-2-carboxylates respectively were synthesized and structurally characterized.3. An improvement, which adopt readily available inorganic base potassium carbonate instead of the organic base, 1,8-diazabicyclo[5.4.0]undec-7-ene(DBU)and easily hydrolyzed potassium tert-butoxide to the Barton-Zard reaction was employed during the synthesis of all the desired 3,4-disubstituted pyrroles.The improved method was flexible and convenient to operate.4. The symmetrical porphyrinβ-3,8,13,18-tetramethyl-2,7,12,17-tetra(4-N,N-diphenyl) phenylporphyrin, was synthesized from ethyl-3-(4-N,N-diphenyl) phenyl-4-methylpyrrole-2- carboxylate through pyrrole self-polymerization. And another unsymmetrical porphyrin,2-(4-N,N-diphenyl)phenyl-3,7,8,17,18-pentamethylporphyrin , was synthesized from 3- (4-N,N-diphenyl)phenyl-4-methylpyrrole through“3+1”approach.5. The spectral properties of 2-(4-N,N-diphenyl)phenyl-3,7,8,17,18-pentamethyl porphyrin andβ-3,8,13,18-tetramethyl-2,7,12,17-tetra(4-N,N-diphenyl) phenylporphyrin were researched and the effect of the porphyrins’structures to spectral properties was discussed.更多还原