Hydrogen peroxide olefin epoxidation, propylene oxide

Epoxidation with hydroperoxides is the basis for the large-scale indirect production of propylene oxide by a process that has been called the Oxirane or Halcon processes. Early work was reported by Smith in a patent issued in 1956 [457], which described soluble heteropoly acids containing transition metals such as chromium, molybdenum, and tungsten that could be employed as homogeneous catalysts for the reaction of olefins with organic hydroperoxides and hydrogen peroxide. 

The TS-1 catalyst has also been found effective in the epoxidation of olefinic compounds. It is of particular interest in the preparation of propylene oxide by oxidation of propylene with hydrogen peroxide (Hoelderich, 1988). Ethylene has also been epoxidized to ethylene oxide with 30% H2O2 in aqueous /-butanol to obtain 96% selectivity at 97% H2O2 conversion (Sheldon, 1991). 

The titanium silicalite is an industrial catalyst for the oxidation of olefins or aromatics with hydrogen peroxide as oxidant. It catalyses the epoxidation of both olefins and diolefins with high yields and with high epoxide selectivity (>98% for propylene). The reaction can be conducted with dilute H2O2 solution in contrast to other competing catalysts, which require nearly pure H2O2 as oxidant. 

Ishii, Y., Yamawaki, K., Ura, T., et al. (1988). Hydrogen Peroxide Oxidation Catalyzed by Heteropoly Acids Combined with Cetylpyridinium Chloride. Epoxidation of Olefins And Allylic Alcohols, Ketonization of Alcohols and Diols, and Oxidative Cleavage of 1,2-Diols and Olefins, J. Org. Chem., 53, pp. 3587-3593 Sato, K., Aoki, M., Ogawa, M., et al. (1997). A Halide-Free Method for Olefin Epoxidation with 30% Hydrogen Peroxide, Bull. Chem. Soc. Jpn., 70, pp. 905-915 Xi, Z. W., Zhou, N., Sun, Y., et al. (2001). Reaction-Controlled Phase-Transfer Catalysis for Propylene Epoxidation to Propylene Oxide, Science, 292, pp. 1139-1141 Neumann, R. 

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