Oxidation reactions with in situ generated oxidants

The main achievements and future prospects of in situ oxidations are discussed, focusing on the advantages and limits of the technique. This is based on hydrogen peroxide, peracids, metal peroxo and metal oxo species, generated in situ by oxygen and a reducing agent: hydrogen, carbon monoxide, metallic iron or zinc, hydrides, aldehydes and other organic reductants. Hydrogen peroxide and hydrogen, respectively, are preferred reagents for the inherent cleanliness of their use, producing only water as the byproduct. Examples are the epoxidation of propylene by air and alkylated anthrahydroquinones, catalysed by titanium silicalite (TS-1), and the hydroxylation of alkanes and aromatics on TS-1 and on other heterogeneous catalysts loaded with noble metals. The halogenation of phenol with hydrogen/oxygen/halogenidric acid mixtures on Pd/TS-1, has also been reported. Carbon monoxide was used to replace hydrogen in in situ oxidations occurring at higher temperatures. Reducing agents other than hydrogen and carbon monoxide lead to the formation of more than stoichiometric amounts of coproducts, which add complexity to the overall process for their separation and recycle/disposal. In the in situ oxidations by GifIII/IV systems and by aldehyde/oxygen mixtures, large amounts of metallic wastes and carboxylic acid are co-produced, respectively, hindering their application in bulk chemicals production. Future developments might arise from the design of superior catalysts both for the in situ generation of hydrogen peroxide or peroxidic species from oxygen/hydrogen mixtures and for its subsequent efficient use. Oxygen/carbon monoxide and nitrous oxide can replace hydrogen/oxygen in oxidations at progressively higher temperatures, albeit no in situ oxidation with N2O as yet has been reported. The general features of hydrogen peroxide and nitrous oxide are briefly compared and discussed.