Photochemical oxidation of fatty acid esters with and without chlorophyll

1. It has been confirmed that the principal products formed in the oxidation of methyl oleate by oxygen under a variety of conditions are predominantlytrans hydroperoxides. However no inversion of the double bond occurs in unoxidized oleate. Hence the conversion ofcis totrans double bonds and peroxide formation occur together in the same molecules.
2. The autoxidation of methyl linoleate at low temperature yields predominantlycis,trans conjugated hydroperoxides. Autoxidation at 25°C., oxidation catalyzed by visible light, or ultraviolet light and copper soap catalyzed oxidation at temperatures appreciably above 0°C., lead to the formation primarily oftrans,trans conjugated hydroperoxides. The inversion of the second double bond in this case appears to be independent of the peroxide-forming reactions.
3. The photochlorophyll oxidation of methyl linoleate leads to the formation of some unconjugated hydroperoxides, some of which containtrans double bonds.
4. Under all of the conditions employed in the present investigation, the oxidation of methyl oleate and linoleate led primarily to the formation of monomeric peroxides which retained most of the unsaturation of the parent compound.