Vanadium compounds, catalysts hydroperoxide

P oly 0 xome tall ate s, derived from both isopoly adds and heteropoly adds, are important homogeneous oxidation catalysts. The metals involved are vanadium, niobium, tantalum, molybdenum, and tungsten. The reactions involved are the oxidation of a wide range of organic compounds by hydrogen peroxide or organic hydroperoxide. 

Organic hydroperoxides are generally used for the preparation of sulfoxides from sulfides, - while sulfones can be obtained in neutral organic solvents in the presence of metal catalysts such as V, Mo and Ti oxides at 50-70 C. Two polymer-supported reagents which involve peroxy acid groups and bound hypervalent vanadium(V) and molybdenum(VI) compounds have been developed for facile oxidation of sulfoxides to sulfones. 

Epoxidation of allylic alcohols with peracids or hydroperoxide such as f-BuOaH in the presence of a transition metal catalyst is a useful procedure for the synthesis of epoxides, particularly stereoselective synthesis [587-590]. As the transition metal catalyst, molybdenum and vanadium complexes are well studied and, accordingly, are the most popular [587-590], (Achiral) titanium compounds are also known to effect this transformation, and result in stereoselectivity different from that of the aforementioned Mo- and V-derived catalysts. The stereochemistry of epoxidation by these methods has been compared for representative examples, including simple [591] and more complex trcMs-disubstituted, rrans-trisubstituted, and cis-trisubstituted allyl alcohols (Eqs (253) [592], (254) [592-594], and (255) [593]). In particular the epoxidation of trisubstituted allyl alcohols shown in Eqs (254) and (255) highlights the complementary use of the titanium-based method and other methods. More results from titanium-catalyzed diastereoselective epoxidation are summarized in Table 25. 

Many other metal ions have been reported as catalysts for oxidations of paraffins or intermediates. Some of the more frequently mentioned ones include cerium, vanadium, molybdenum, nickel, titanium, and ruthenium [21, 77, 105, 106]. These are employed singly or in various combinations, including combinations with cobalt and/or manganese. Activators such as aldehydes or ketones are frequently used. The oxo forms of vanadium and molybdenum may very well have the heterolytic oxidation capability to catalyze the conversion of alcohols or hydroperoxides to carbonyl compounds (see the discussion of chromium, above). There is reported evidence that Ce can oxidize carbonyl compounds via an enol mechanism [107] (see discussion of manganese, above). Although little is reported about the effectiveness of these other catalysts for oxidation of paraffins to acetic acid, tests conducted by Hoechst Celanese have indicated that cerium salts are usable catalysts in liquid-phase oxidation of butane [108]. 

In a recent paper the interaction of tert-butyl hydroperoxide with oxide catalysts was investigated. This oxidant is used, with the aid of oxide catalysts, for the oxidation of (benzo) thiophenes to the corresponding sulfones in liquid phase, but also for other liquid-phase oxidation and epoxidation reactions. The adsorption of tert-butyl hydroperoxide on zirconia from the gas-phase is reported to produce an undissociated adsorbed species as well as a terbutylperoxide species whose 00 stretching frequency is observed at 867 cm i.e. shifted to higher frequencies with respect to the undissociated compound (845 cm ). The presence of vanadium at the surface of the catalyst increases the reactivity of this species. 

The catalysts of this process are vanadium, molybdenum, tungsten, niobium, chromium, and titanium compounds. The yield of oxide calculated per olefin is close to 100%, and that per hydroperoxide reaches 85—95% and depends on the catalyst, temperature, and depth of conversion. 

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