Copper Mediated Epoxidation of high Oleic Natural Oils with a Cumene–O2 System
Nicola Scottia, Nicoletta Ravasioa, Rinaldo Psaroa, Claudio Evangelistia, Sylwia Dworakowskab, Dariusz Bogdalb, Federica Zaccheriaa
a CNR Istituto di Scienze e Tecnologie Molecolari, Milano, Italy
b Department of Biotechnology and Physical Chemistry, Faculty of Chemical Engineering and Technology, Cracow University of Technology, Cracow, Poland

Substrate	Catalyst	Time (h)	Conv. (%)	Sel. (%)	
Methyl 
Oleate	CuO/Al2O3	6	98	86	
	CuO/PVPy	8	99	88	
Sunflower highlyoleic	CuO/Al2O3	6	99	78	
	CuO/PVPy	7	96	89	
Stabilised Soybean	CuO/Al2O3	6	98	79	
	CuO/PVPy	9	81	80	
Stabilised Rapeseed	CuO/Al2O3	7	95	79	
	CuO/PVPy	9	99	82	
Table 1. One-pot epoxidation of MO and natural derived FAMEs	
Epoxidation is one of the oleo chemical industry processes requiring a more environmentally friendly approach. This reaction leads to a wide series of high added-value compounds and intermediates. However, the synthesis of epoxidized vegetable oils still relies on the use of in situ generated peracids[1]. Some of us recently reported on the epoxidation of olefins by using a CuO/Al2O3 catalyst and cumene in the presence of O2[2]. Here we wish to report that a similar approach can be conveniently used in the epoxidation of fatty acid methyl esters, over CuO/Al2O3 and CuO/PVPy (PVPy = polyvinylpyridine) catalysts. Very high yields of epoxy stearate were obtained for methyl oleate, high-oleic sunflower oil fatty acid methyl-esters (FAMEs) and “stabilized”[3] rapeseed and soybean oil FAMEs (Table 1). The reaction proceeds through the catalyzed reaction between O2 and cumene to give cumyl hydroperoxide which is the active epoxidation species (as in the Sumitomo process for the production of propylene oxide)[4]. 

[1] H. Baumann, M. Bühler, H. Fochem, F. Hirsinger, H. Zoebelein, J. Falbe, Angew. Chem. Int. Ed. Engl., 1988, 27, 41.
[2] N. Scotti, N. Ravasio, F. Zaccheria, R. Psaro, C. Evangelisti, Chem. Commun., 2013, 49, 1957.
[4] N. Ravasio, R. Psaro, F. Zaccheria, P. Bondioli, Eur. J. Lipid Sci. Technol., 2012, 114, 24 
[3] N. Scotti, N. Ravasio, R. Psaro, C. Evangelisti, S. Dworakowska, D. Bogdal, F. Zaccheria, Catal. Commun., 2015, 64, 80.