水溶性卟啉催化氧化1,5-萘二酚  

Catalysis of Water-soluble Porphyrins for Oxidation of 1,5-Dihydroxynaphthalene

作　　者：侯宗胜[1] 任奇志[1] 王颖[1] 章虹[1] 

机构地区：[1]上海交通大学化学化工学院,上海200240

出　　处：《高等学校化学学报》2011年第10期2353-2359,共7页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:20871082;20471037)资助

摘　　要：合成并表征了系列水溶性卟啉配体[H2TPPS:5,10,15,20-四-(4-磺酸基苯基)-21H,23H-卟啉,H2TMPyP:5,10,15,20-四(4-吡啶基)-21H,23H-卟啉,H2TCPP:5,10,15,20-四-(4-羧基苯基)-21H,23H-卟啉]及相应的铁、锌及钴配合物.将水溶性卟啉作为光敏剂,用于1,5-萘二酚的光催化反应,产物为5-羟基-1,4萘醌.利用UV-Vis方法对卟啉催化1,5-萘二酚的反应过程进行了监测,探索了水相和水/二氯甲烷双相催化体系,确定了较为理想的反应条件.探讨了不同取代基和不同金属离子对卟啉催化性能的影响,初步讨论了催化机理.结果表明,具有磺酸根阴离子取代基的水溶性卟啉具有最好的催化活性;卟啉的催化活性与其在反应体系中的稳定性密切相关;铁卟啉在反应初期呈现很高的催化活性,但在光照条件下容易发生光解而导致催化活性的降低;无金属的磺酸卟啉在催化体系中的催化活性和稳定性最好.A series of water-soluble free base porphyrins（H2TPPS,H2TCPP and H2TMPyP） and their metal complexes（FeTPPS,ZnTPPS,CoTPPS） were efficiently synthesized and characterized.As photosensitizers,these porphyrins were used to catalyze the oxidation of 1,5-dihydroxynaphthalene under visible light irradiation.The main product were identified as 1,5-dihydroxynaphthalene.The catalytic process was monitored by UV-Vis method and the optical catalytic conditions were established.The water phase system and water-dichloromethane double phase system were explored.The effects of various factors such as substituent groups,central metal ions were investigated.The catalytic results show that anionic porphyrins have efficient catalytic activity;At the beginning of the reaction,high catalytic acitivity can be obtained for iron porphyrin,while it decreases greatly because of catalyst photolysis;The sodium sulfonic porphyrin is the most stable catalyst in the reaction system and has the best catalytic activity.

关 键 词：水溶性卟啉 氧化 1 5-萘二酚 催化 

分 类 号：O643[理学—物理化学] O614[理学—化学]