Synthesis of Iron Chlorophyllins and Their Catalytic Performance for Aerobic Oxidation of Cyclohexene
Synthesis of Iron Chlorophyllins and Their Catalytic Performance for Aerobic Oxidation of Cyclohexene作者机构：College of Chemistry and Chemical Engineering Hunan University Changsha 410082 P. R. China
出 版 物：《Chemical Research in Chinese Universities》 (高等学校化学研究（英文版）)
年 卷 期：2013年第29卷第3期
页 面：526-532页
核心收录：
学科分类：081702[工学-化学工艺] 081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学] 070301[理学-无机化学]
基 金：Supported by the National Natural Science Foundation of China(No.20606008)
主 题：Chlorophyll Iron chlorophyltin Air Cyclohexene Catalytic oxidation
摘 要：A series of iron（III） chlorophyllins was prepared from silkworm excrement crude chlorophyll extract as a raw material. Aerobic oxidation of cyclohexene by using the prepared iron（III） chlorophyllins as biomimetic catalysts was studied under atmospheric pressure in the absence of reducing agent and solvent. The results indicate that chloro- phyll iron porphyrins have better catalytic performance than the industrial-applied iron tetraphenylporphyrin and cobalt tetraphenylporphyrin, and possess a higher selectivity for 2-cyclohexen-1-one. The smaller the polarity of iron（III） chlorophyllin＇s ligand is, the easier the catalytic oxidation of cyclohexene will be. Esterification products of iron（III） chlo- rophyllins can catalyze the oxidation of cyclohexene better than non-esterified iron（III） chlorophyllins, and therefore show a higher conversion of cyclohexene and a higher selectivity for 2-cyclohexen-l-one than the non-esterified ones. Among the six synthesized iron（III） chlorophyllin catalysts, iron（III） methyl-pyropheophorbide-a is the best biomimetic catalyst for the highest conversion of cyclohexene. The influences of catalyst＇s substituent, polarity and ring structure on the catalytic performance were discussed. The catalytic performance of iron（III） chlorophyllins improves with decreasing polarity, increasing conjugated degree of porphyrin＇s ring or enhancing chlorophyllins＇ stability. Possible mechanism of cyclohexene aerobic oxidation catalyzed by iron（III） chlorophyllins was also discussed.
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