A Halide-Free Method for Olefin Epoxidation with 30% Hydrogen Peroxide

• Published in: Bulletin of the Chemical Society of Japan 1997-04, Vol.70 (4), p.905-915
• Main Authors: Sato, Kazuhiko, Aoki, Masao, Ogawa, Masami, Hashimoto, Tadashi, Panyella, David, Noyori, Ryoji
• Format: Article
• Language: English
• ISSN: 0009-2673; 1348-0634
• DOI: 10.1246/bcsj.70.905

A catalytic system consisting of sodium tungstate dihydrate, (aminomethyl)phosphonic acid, and methyltrioctylammonium hydrogensulfate, effects the epoxidation of olefins using 30% hydrogen peroxide with a substrate-to-catalyst molar ratio of 50—500. The reaction proceeds in high yield without solvents, or, alternatively, with added toluene under entirely halide-free conditions. Lipophilic ammonium hydrogensulfate, which replaces the conventional chloride, and an (α-aminoalkyl)phosphonic acid are crucial for the high reactivity. This method is operationally simple, environmentally benign, and much more economical than the oxidation with m-chloroperbenzoic acid, allowing for a large-scale preparation of epoxides. Various substrates including terminal olefins, 1,1- and 1,2-disubstituted olefins, cyclic olefins, and tri- and tetrasubstituted olefins as well as allylic alcohols, esters, α,β-unsaturated ketones, and ethers can be epoxidized in high yield. The scope and limitations of this new reaction system are discussed.