Petroleum Chemistry, Vol.46, No.3, 167-170, 2006
Hydrogen peroxide oxidation of 2-cyanoethanol catalyzed by metal complexes
Oxidation of 2-cyanoethanol, a relatively inert primary alcohol, with several systems (both homogeneous and heterogenized) based on transition metal complexes was studied. The oxidation was performed under homogeneous conditions with 35% hydrogen peroxide upon catalysis by the chlorides FeCl3 or OsCl3 The best result was obtained upon the oxidation catalyzed by OsCl3 at 70 degrees C for 3 h in the absence of solvent: the total yield of the corresponding aldehyde and cyanoacetic acid reached 90%, and the turnover number was 1500. The systems [LMnIV(O)(3)(MnL)-L-IV](n)(X)(m)-oxalic acid (where L = 1,4,7-trimethyl-1,4,7-triazacyclononane) also catalyze oxidation of 2-cyanoethanol with yields of 50-70% either under homogeneous conditions (X = PF6-, n = 1, and m = 2) or with the use of the catalyst in the heterogenized form (as insoluble heteropoly acid salt), where X = W12SiO404-, n=2, and m=1.