Oxidation of C-1-C-4 alcohols by iron- and ruthenium-sulfophthalocyanine precatalysts with hydrogen peroxide or mono-persulfate in water

A catalytic system consisting of iron-or ruthenium-sulfophthalocyanine and hydrogen peroxide or mono-persulfate was effective in the oxidation of simp le primary and secondary alcohols as well as of simple ketones. The oxidati on reactions were conducted in aqueous media with turnover rates, defined a s moles of product per mole of catalyst per minute, up to 5. Primary alcoho ls, including methanol, were selectively oxidized into the corresponding ca rboxylic acids. Secondary alcohols were transformed into the corresponding ketones, which were found to undergo further oxidation to esters via Baeyer -Villiger reaction, followed by hydrolysis or alternatively in the case of acetone via direct oxidation to acetic acid and CO2 - Moreover, t-butyl alc ohol was also found to be slowly oxidized into acetone and methanol. Analys is of the oxidation reaction of cyclobutanol indicated an ionic mechanism; no deuterium kinetic isotope effect was measured in the cases of methanol a nd ethanol. The mechanistic origin of the catalytic efficiency is also disc ussed. (C) 2001 Elsevier Science B.V. All rights reserved.