Stoll M S, Gray C H
Biochem J. 1977 Apr 1;163(1):59-101. doi: 10.1042/bj1630059.
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.
结果表明，用稀钠汞齐短暂还原胆红素可得到同时含有乙烯基和亚乙基β-取代基的色原。这些色原与胆红素或中胆红素经酸催化重排，随后脱氢，得到一系列含有未共轭亚乙基和乙烯基取代基的新紫红素。中胆素原、胆红素和中胆红素之间的重排产生了IIIα、IXα和XIIIα系列的二氢胆红素紫红素、中胆红素紫红素、胆绿素、二氢胆绿素和中胆绿素。通过这种方法制备了30种化合物，通过薄层层析作为二甲基酯进行纯化，并通过核磁共振、质谱和电子光谱以及化学相互转化和降解进行表征。
