【作者】 陈玉芸；

【导师】 佘远斌； 李惕川；

【作者基本信息】 北京工业大学 ， 环境工程， 2000， 硕士

【摘要】 金属卟啉类化合物（包括金属酞菁）是一类结构非常特殊的化合物，它们具有许多独特的性质，应用也十分广泛。其主要用途之一是作为模拟生物酶催化剂，催化氧气液相选择氧化饱和烃或芳烃及其侧链使之功能化。在金属卟啉类化合物中，由于中心金属离子的种类、卟啉及酞菁环外取代基以及轴向配体的性质对其催化氧化性能都有影响。因此，可通过有针对性地调变中心金属离子，以及在卟啉环外或轴向引入不同取代基等方法来改变其催化氧化性能。 本论文基于上述三个方面的考虑，设计了九个系列共40个中心金属离子和外环结构不同的金属卟啉类催化剂，并合成了其中的二个系列共十二个金属卟啉和金属酞菁催化剂。同时，对所合成催化剂的结构及其催化氧化性能进行了表征。 本文首先以偏苯三甲酸酐、尿素和金属盐为原料合成了铁、钻、铜、锌四个四羧基金属酞菁催化剂，并采用红外、紫外-可见光谱、质谱等分析手段对其主要的官能团及结构进行了鉴定，证实所合成的化合物确为四羧基金属酞菁化合物。 其次，以邻（对）氯苯甲醛、吡咯和金属盐为原料合成了铁、钻、铜、锌八个四-（邻/对-氯苯基）金属卟啉催化剂，其中五个是文献尚未报道过的新化合物，并采用红外、紫外-可见光谱、质谱对其主要官能团及结构进行了表征。同时，采用高分辨质谱对五个新化合物的结构进行了鉴定。证实所合成的化合物确为四-（邻/对-氯苯基）金属卟啉化合物。 最后以氧气液相氧化邻硝基甲苯制取邻硝基苯甲酸为模型反应，在40℃，3MPa的温和条件下，考察了十二个金属卟啉类催化剂的催化氧化性能。发现不加催化剂则得不到目标产物邻硝基苯甲酸，而加入以上十二个催化剂中的任何一个，均可使邻硝基苯甲酸的收率超过40％。这说明所合成的十二个催化剂对上述反应均有显著的催化氧化活性。而且，当中心金属离子相同时，上述催化剂的催化氧化活性次序依次为：四-（邻-氯苯基）金属卟啉＞四-（对-氯苯基）金属卟啉＞四羧基金属酞菁；当配体相同、中心金属离子不同时，其催化氧化活性次序依次为：Co＞Zn＞Cu＞Fe；另外，在所有催化剂中，四-（邻-氯苯基）钴卟啉的催化活性最佳，可使邻硝基苯甲酸的最大单程收率达到66.8％。以上结果说明，中心金属离子的种类、母体环性质及其环外取代基的位置不同，均会影响金属卟啉类催化剂的催化氧化性能。更多还原

【Abstract】 Porphyrin-like compounds (including metal phthalocyanines) are compounds with special structure and unique characters. They are widely used in many fields, especially as important mimic enzyme catalysts which catalyze the selective oxidation functionallization of saturated hydrocarbons, aromatic hydrocarbons and its side chain with 02. Because different central metal ions, substituents at phenyl rings of porphyrin and axial ligands have significant effects on their atJ tic activity, so that we can improve their catalytic activity by adjusting central metal ions, introducing various substituents on phenyl rings and axis of porphyrin-like compounds. Basis on the described ideas, 9 series and altogether 40 porphyrin-like compounds with different structures or center metal ions were designed, and two series and altogether 12 porphyrin-like compounds were synthesized, and the structures and catalytic activities of these catalysts were characterized. Firstly, four 2,9,16,23-tetracarboxylicphthalocyanines of Co, Fe, Cu, Zn were synthesized from trimellitic anhydride, urea, and metal salts. The structures of these compounds were characterized and confirmed by JR. UV-Vis and MS. Secondly, eight tetra-(o/p-chlorophenyl) porphyrins of Co, Fe, Cu and Zn were synthesized from oip -chloro-benzaldehydes, pyrrole and metal salts, in which five are new compounds which were not reported by literatures so far. The structures of these compounds were determined by JR. UV-Vis and MS. The structures of 5 new compounds were further confirmed by High Resolution Mass Spectrum. Catalytic activities of these compounds were investigated by means of dioxygen liquid-phase oxidation of o -nitrotoluene to o-nitrobenzoic acid at the mild conditions of4OXD and 3MPa. It was found that o-nitrobenzoic acid could not be obtained from oxidation of o-nitrotoluene when no catalyst. The yield of o-nitrobenzoic acid all can reach more than 40% by using anyone of 12 catalysts synthesized. The results showed that all 12 catalysts synthesized had significant catalytic activity for above reaction. And, when the center metal ions are identical, the activity order of 12 catalysts is: tetra-(o-chlorophenyl) metal porphyrins> tetra-(o-chlorophenyl) metal porphyrins > metal phthalocyanine tetracarboxylic acids; When the ligands are the same and central metal ions are different, the catalytic activity sequence of 4 metal complexes is Co > Zn> Cu> Fe; In addition, the catalytic activity of tetra-(o-chlorophenyl) cobalt porphyrin was the best among 12 metal porphyrin-like compounds, and the yield in 66.8% of o-nitrobenzoic acid was obtained. The above-listed results showed that kinds of the center mental ions, properties of parent rings and the positions of substituents all had some effect on catalytic oxidation performance of metal porphyrin-like compounds更多还原