Boreskov Institute of Catalysis of the Siberian Branch of Russian ...

PP-III-36THE ORGANIC COMPOUNDS OXIDATION PROCESSES AT THEPRESENCE OF HOMOGENEOUS CATALYSTSN.V. Selivanova, P.V. Berdnikova, and Z.P. PaiBoreskov Institute of Catalysis SB RA S, Prosp. Akad. Lavrentieva, 5,Novosibirsk 630090 RussiaFax: +7(383) 330 8056. E-mail: natas@catalysis.ruThe unsaturated organic compounds oxidation into their corresponding epoxides orcarboxylic acids plays a central role in fine chemicals manufacture. Traditionally, suchtransformations involve multi-step synthesis or have been performed with inorganic oxidant(ozone, potassium permanganate, alkaline-earth metal chlorides, promoted by chlorinecontainingsubstances, etc.) or organic hydroperoxides [1, 2]. The selectivity of thesereactions to target product is not high because of the formation of a large amount of byproducts.In the oxidation processes of organic compounds it is important to replace ofstoichoimetric oxidation by catalytic oxygen transfer processes in combination with oxygendonor like for example hydrogen peroxide because it is very attractive from a synthetic andindustrial viewpoint since this reagent is relatively inexpensive, and environmentally clean.Metal complexes are mainly used as catalysts in these reactions. Utilization of catalyticproperties of the metal complexes is of particular importance in the performance of liquidphasereactions in two-phase systems.It is common knowledge that different organic substrates (olefins, alcohols, aromatichydrocarbons) may be oxidized at presence of tungsten peroxocomplexes, PW x O z– y , whichform in the systems: H 2 O 2 – H 3 PO 4 – Na 2 WO 4 and H 3 PW 12 O 40 – H 2 O 2 [3]. In situ synthesis ofthe catalyst is accompanied by formation of a mixture of peroxopolyoxometallates (PPOM)such as PO 4 [WO(O 2 ) 2 ] 4 } 3– , [W 2 O 3 (O 2 ) 4 (H 2 O) 2 ] 2– , {HPO 4 [WO(O 2 ) 2 ] 2 } 2– [2]. Note thattetrakis(oxodiperoxotungsto)phosphate {PO 4 [WO(O 2 ) 2 ] 4 } 3– exhibits the highest catalyticactivity. In this work we used a number of catalysts based on the above PPOM anion andphase transfer catalysts being quarternary ammonium salts (QAS). Such catalytic systemspermit one to develop new efficient approaches to synthesis of a series of practically valuablealiphatic and aromatic epoxides as well as mono-, di- and polycarboxylic acids via directoxidation of various organic substrates with hydrogen peroxide.The advantages of this method are that the process occurs in one step, in mild conditions,is efficient and ecologically safe, and requires inexpensive reagents.Thus, the reactions of oxidation of organic materials by hydrogen peroxide in the twophaseconditions (organic phase – aqueous phase) predominantly proceeds in the organic371