| 金属四苯基卟啉-次氯酸钠模拟体系中芳醛氧化反应的研究 |
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| 引用本文： | 李存发,郑维忠,王先元,李广年.金属四苯基卟啉-次氯酸钠模拟体系中芳醛氧化反应的研究[J].有机化学,1993,13(2):139-145. |
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| 作者姓名： | 李存发 郑维忠 王先元 李广年 |
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| 作者单位： | 中国科学院成都有机化学研究所，中国科学院成都有机化学研究所，中国科学院成都有机化学研究所，中国科学院成都有机化学研究所 四川，成都，610015 中国科学院上海有机化学研究所金属有机开放实验室，上海，200032，四川，成都，610015 中国科学院上海有机化学研究所金属有机开放实验室，上海，200032，四川，成都，610015 中国科学院上海有机化学研究所金属有机开放实验室，上海，200032，四川，成都，610015 中国科学院上海有机化学研究所金属有机开放实验室，上海，200032 |
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| 摘 要： | 研究了以次氯酸钠为氧化剂在两相条件下芳香醛氧化反应中锰(III)-卟啉的催化性质, 在TPPMn(III)醋酸盐, TPPFe(III)氯化物, TPPCo(II)和TPPNi(II)催化剂中(四苯基卟啉, TPP), 前二个化合物呈现催化活性, 研究表明, OXO-金属卟啉的形成是反应的关键步骤。
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| 关 键 词： | 催化 氧化 氯化物 次氯酸钠 铁络合物 金属络合物 苯甲醛 锰络合物 乙酸盐 卟啉 |
Oxygenation of aromatic aldehydes by the metallotetraphenylporphyrin-sodium hypochlorite system |
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| LI Cun-Fa,ZHENG Wei-Zhong,WANG Xian-Yuan,LI Guang-Nian Chengdu Institute of Organic Chemistry,Academia Sinica, Chengdu,Sichuan, Laboratory of Organometallic Chemistry.Oxygenation of aromatic aldehydes by the metallotetraphenylporphyrin-sodium hypochlorite system[J].Chinese Journal of Organic Chemistry,1993,13(2):139-145. |
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| Authors: | LI Cun-Fa ZHENG Wei-Zhong WANG Xian-Yuan LI Guang-Nian Chengdu Institute of Organic Chemistry Academia Sinica Chengdu Sichuan Laboratory of Organometallic Chemistry |
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| Institution: | LI Cun-Fa,ZHENG Wei-Zhong,WANG Xian-Yuan,LI Guang-Nian Chengdu Institute of Organic Chemistry,Academia Sinica,610015 Chengdu,Sichuan, Laboratory of Organometallic Chemistry,Shanghai Institute of Organic Chemistry,Academia Sinica,200032 Shanghai |
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| Abstract: | The catalytic behaviors of Mn(III)-porphyrin in the oxidation of aromatic aldehydes with NaOCl as oxidant under two-phase condition have been investigated. When TPPMn(III)OAc (TPP = tetraphenylporphyrin), TPPFe(III)Cl, TPPCo(II), and TPPNi(II) were used as catalysts, only TPPMn(III)OAc and TPPFeCl exhibit distinct activities. With TPPMn(III)OAc as catalyst, UV - visible spectral changes of the fourth band from 425 nm to 478 nm were observed during the course of the oxygen transfer, suggesting that oxo-manganese(V) porphyrin is the key element for the oxygenation of aldehydes. Electron withdrawing para-substituents of TPPMnOAc lead to an increase in activities and stabilities. Electron withdrawing ortho substituents increase the stabilities of manganese porphyrins, but decrease their activities. |
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| Keywords: | metalloporphyrin aldehyde oxidation catalysis |
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