Mechanism of the catalytic epoxidation of olefins by hydroperoxides in the presence of complex compounds of Mo(VI)
- 30 Downloads
Tert-butyl hydroperoxide in benzene and dichloroethane solutions forms intrasphere coordination compounds with dioxobis-(1, 2-cyclohexanediolate)-molybdenum (VI).
A mechanism was proposed for the epoxidation of olefins by complex compounds of Mo (VI), including the formation of complexes of ROOH with bis-(diolates) Mo(VI). In the second step of the process, hydroperoxide reacts with diol in the coordination sphere of molybdenum with the formation of alcohol and the conversion of the diol to the corresponding oxide.
The paramagnetic complexes recordable in the system tert-butyl hydroperoxide-MoO2L2 do not participate in epoxidation. The increase in the concentration of such complexes in the presence of alcohol is one of the possible causes of the inhibition of reactions of epoxidatien by alcohols.
KeywordsOxide Alcohol Benzene Molybdenum Hydroperoxide
Unable to display preview. Download preview PDF.
- 1.E. S. Gould, R. R. Hiatt, and K. C. Irwin, J. Amer. Chem. Soc.,90, 4573 (1968).Google Scholar
- 2.M. I. Farberov, L. V. Mel'nik, B. N. Bobylev, and V. A. Podgornova, Kinetika i Kataliz,12, 1144 (1971).Google Scholar
- 3.N. M. Emanuel, Z. K. Maizus, and I. P. Skibida, Angew. Chemie,81, 91 (1969).Google Scholar
- 4.G. M. Bulgakova, I. P. Skibida, E. G. Rukhadze, and G. P. Talyzenkova, Kinetika i Kataliz,12, 359 (1971).Google Scholar
- 5.G. M. Bulgakova, A. N. Shupik, I. P. Skibida, K. I. Zamaraev, and Z. K. Maizus, Dokl. Akad. Nauk SSSR,199, 376(1971).Google Scholar
- 6.K. B. Sharpless, J. M. Townsend, D. R. Williams, J. Amer. Chem. Soc.,94, 295 (1972).Google Scholar
- 7.R. B. Svitych, O. P. Yablonskii, A. A. Petukhov, V. A. Belyaev, and A. L. Buchachenko, in: Investigation and Development of the Technology of Processes of Production of Monomers for Synthetic Rubbers [in Russian], Yaroslavl' (1973), p. 116.Google Scholar
- 8.P. Koch and I. Skibida, Gazz. Chim. Ital,104, 225 (1974).Google Scholar
- 9.E. T. Denisov, Handbook. Rate Constants of Homolytic Liquid Phase Reactions [in Russian], “Nauka” (1971).Google Scholar
- 10.A. M. Matucci and E. Perotti, Ger. Pat., 1944925; Chem. Abstrs.,73, 19010 (1972).Google Scholar
- 11.R. A. Sheldon, Recueil Trav. Chim.,92, 253, 367 (1973).Google Scholar