Hydrogen Peroxide Oxidation of Olefins into Carboxylic Acids Catalyzed by Heteropoly Acids

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The conversion of olefins into the corresponding carboxylic acids has much interest from synthetic and industrial points of view. This work is directed toward the development of catalyst to carry out the conversion of olefins into carboxylic acids. Heteropoly acids, especially tris(cetylpyridinium)12-tungsto- phosphate(CWP), [pi-C_5H_5N^+(CH_2)_<15>CH_3]_3[PW_<12>O_<40>]^<3->, synthesized readily from 12-tungstophosphoric acid and 3 equivalents of cetylpyridinium chloride, were found to catalyze the oxidative cleavage of olefins into carboxylic acids with 35% hydrogen peroxide under homogeneous conditions using tert-butyl alcohol as solvent. In the similar manner as CWP, tungstic acid (H_2WO_4) was also effective for the same reaction in tert-butyl alcohol controlled to pH 4-5. This method is especially of interest from the industrial aspect, since non-toxic tungsten can be used as the catlyst.Further, hydrogen peroxide oxidation of a variety of organic substrates was examined by using CWP as catalyst, and the following results were obtained.1. alpha,beta-Unsaturated carboxylic acids were oxidized in water controlled to pH 6-7 to give epoxy carboxylic acids in good yields. 2.1,2-Diols were converted into the corresponding carboxylic acids. 3. alpha,omega-Diols underwent the oxidative dehydrogenation to give lactones in fair to good yields. 4. sec-Alcoholic functions of alcohols and diols were converted into the corresponding carbonyl compounds.The hydrogen peroxide oxidations catalyzed by 12-tungstophosphoric acid combined with cetylpyridinium chloride are attractive as a new catalysis of heteropoly acids.