Epoxidation tungsten

The tert-huty hydroperoxide is then mixed with a catalyst solution to react with propylene. Some TBHP decomposes to TBA during this process step. The catalyst is typically an organometaHic that is soluble in the reaction mixture. The metal can be tungsten, vanadium, or molybdenum. Molybdenum complexes with naphthenates or carboxylates provide the best combination of selectivity and reactivity. Catalyst concentrations of 200—500 ppm in a solution of 55% TBHP and 45% TBA are typically used when water content is less than 0.5 wt %. The homogeneous metal catalyst must be removed from solution for disposal or recycle (137,157). Although heterogeneous catalysts can be employed, elution of some of the metal, particularly molybdenum, from the support surface occurs (158). References 159 and 160 discuss possible mechanisms for the catalytic epoxidation of olefins by hydroperoxides. 

Liquid-Phase Epoxidation with Hydroperoxides. Molybdenum, vanadium, and tungsten have been proposed as Hquid-phase catalysts for the oxidation of the ethylene by hydroperoxides to ethylene oxide (205). tert- uty hydroperoxide is the preferred oxidant. The process is similar to the arsenic-catalyzed route, and iacludes the use of organometaUic complexes. 

Epoxidation systems based on molybdenum and tungsten catalysts have been extensively studied for more than 40 years. The typical catalysts - MoVI-oxo or WVI-oxo species - do, however, behave rather differently, depending on whether anionic or neutral complexes are employed. Whereas the anionic catalysts, especially the use of tungstates under phase-transfer conditions, are able to activate aqueous hydrogen peroxide efficiently for the formation of epoxides, neutral molybdenum or tungsten complexes do react with hydrogen peroxide, but better selectivities are often achieved with organic hydroperoxides (e.g., TBHP) as terminal oxidants [44, 45],... 

With regard to the use of tungsten-based systems, Payne and Williams reported on the selective epoxidation of maleic, fumaric, and crotonic acids with a catalytic amount of sodium tungstate (2mol%) in combination with aqueous hydrogen... 

A particularly interesting system for the epoxidation of propylene to propylene oxide, working under pseudo-heterogeneous conditions, was reported by Zuwei and coworkers [61]. The catalyst, which was based on the Venturello anion combined with long-chained alkylpyridinium cations, showed unique solubility properties. I11 the presence of hydrogen peroxide the catalyst was fully soluble in the solvent, a 4 3 mixture of toluene and tributyl phosphate, but when no more oxidant was left, the tungsten catalyst precipitated and could simply be removed from the... 

The outstanding chemoselectivity of Cp2TiCT was amply demonstrated by Merlic [50,51] and by Dotz [52] who employed a, /3-unsaluraled tungsten and chromium carbenes as radical traps for C - C bond formation. In the latter contribution the very acid sensitive glycal epoxides were used with good success. An example is shown in Scheme 8. 

SMPO [styrene monomer propylene oxide] A process for making propylene oxide by the catalytic epoxidation of propylene. The catalyst contains a compound of vanadium, tungsten, molybdenum, or titanium on a silica support. Developed by Shell and operated in The Netherlands since 1978. 

Tungsten-based catalysts including POMs show high efficiency of H202 utilization [17,18,78-100]. Ishii and coworkers [18] have reported effective H202-based epoxidation of alkenes catalyzed by H3PW12O40 combined with cetyl pyridinium chloride (CPC) as a phase-transfer agent ... 

Selected examples of the tungsten(Vl) promoted epoxidation of allcenes by hydrogen peroxide... 

The reaction sequence is summarized below using isobucane as the hydrocarbon. The crucial and nearly incredible part of the process is in two parts itself but only shows as one. It is the second equation where the oxygen molecule transfers to the propylene molecule and the ring closes to form the epoxide. (Thats why they call it epoxidation). The magic that causes all that to happen is in the metal catalysts, molybdenum naphthenate or the soluble salts of titanium, vanadium, or tungsten. This molecular fancy-dance is but one of nniany examples in chemistry where catalysts can cause atoms to slide around molecules in unlikely ways. 

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