Brief reduction of bilirubin with dilute sodium amalgam was shown to give chromogens containing both vinyl and ethylidene beta-substituents. Acid-catalysed rearrangement of these chromogens with bilirubin or mesobilirubin and subsequent dehydrogenation gave a range of new violins containing unconjugated ethylidene and vinyl substitutents. Rearrangements between mesobilirubinogen, bilirubin and mesobilirubin gave dihydrobiliviolins, mesobiliviolins, biliverdins, dihydrobiliverdins and mesobiliverdins of the IIIalpha, IXalpha and XIIIalpha series. In this way 30 compounds were prepared, purified by t.l.c. as dimethyl esters, and characterized by n.m.r., mass and electronic spectroscopy, and by chemical interconversion and degradation.
