The effect Of Solvent on Competing Hydroperoxide and Dioxetane Formation on Photo-Sensitized Oxygenation of Olefins

Article abstract of DOI:10.1002/hlca.19820650113

The rates of the competitive photo-sensitized oxygenation of 2-isobutylidene-adamantane (1) and 2-propylidene-adamantane (2) with 1,1-di-t-butyl-2-methoxyethene (3) in various solvents were determined.The rates for 1 and 2 were independent of solvent, whereas that for 3 varied markedly with solvent polarity.Compounds 1 and 2 gave only hydroperoxides while 3 gave dioxetane.These results are interpreted in terms of two competing processes involving little and much charge separation leading to hydroperoxide and dioxetane, respectively.