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Catalytic epoxidation of fatty acid methyl esters by modified metalloporphyrins with variable metals and electron-donating substituents

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Abstract

The catalytic efficiency of modified tetraphenylporphyrins with various metals (Mn, Fe, Co, Ni and Zn) and different electron-donating substituents (–OCH3, –OH, –N(CH3)2, –SO3Na) at the phenyl para-positions using hydrogen peroxide (H2O2, 30 wt%) as the oxidant has been researched in the epoxidation of unsaturated fatty acid methyl esters (FAMEs) under mild conditions. In the present system, the co-catalyst effect of inorganic salts had a crucial role in enhancing catalytic performance. According to the yields, the catalytic activities of metalloporphyrins were in the following order: Mn(TPP)Cl ≈ Fe(TPP)Cl > CoTPP > NiTPP > ZnTPP, and Mn(TPP)Cl > Mn(TMOPP)Cl ≈ Mn(THPP)Cl > Mn(TDMPP)Cl > Mn(TPPS4)Cl. Moreover, metalloporprhyrins after modification by electron-donating substituents displayed promoted thermolysis temperatures. Remarkably, the formation of intermediate porMnV=O has also been indicated, which was verified by both a kinetic study of FAMEs epoxidation and UV–Vis spectroscopy.

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Acknowledgments

This work was supported financially by the National “Twelfth Five-Year” Plan for Science & Technology (2012BAD32B03), the National Natural Science Foundation of China (20903048) and the Innovation Foundation in Jiangsu Province of China (BY2013015-10).

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Authors and Affiliations

  1. The Key Laboratory of Food Colloids and Biotechnology, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi, 214122, People’s Republic of China

    Weijie Zhang, **** Jiang, Jianghao Wu & **bo Zhang

  2. Technology, Policy and Management, Technische Universiteit Delft, Tilburg, The Netherlands

    Kelei Jiang

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  1. Weijie Zhang
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Correspondence to **** Jiang.

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Zhang, W., Jiang, P., Wu, J. et al. Catalytic epoxidation of fatty acid methyl esters by modified metalloporphyrins with variable metals and electron-donating substituents. Reac Kinet Mech Cat 112, 147–158 (2014). https://doi.org/10.1007/s11144-014-0676-4

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  • DOI: https://doi.org/10.1007/s11144-014-0676-4

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