Direct Photoisomerization of Benzalpyrrolinone and Oxidipyrromethene Models for Bilirubin

Direct photoisomerizations of benzalpyrrolinones yield the corresponding E-isomers via a singlet state, since no effect of oxygen on the reaction rates was observed. The Z-oxodipyrromethene was photoisomerized to the E-isomer in a degassed system. In an aerobic system the oxodipyrromethene 3 was photoisomerized at the early stage of the reaction and photooxygenated slowly at latter stage of the reaction. For bilirubin, other (possibly Z ${\to}$ E) than self-sensitizing $^1O_2$ reaction should have occurred because of the lack of a solvent effect on the self-sensitized photooxidation reaction rate at the early stage.