Fukuhara K, Miyata N
National Institute of Health Sciences, Tokyo, Japan.
Chem Res Toxicol. 1995 Jan-Feb;8(1):27-33. doi: 10.1021/tx00043a003.
Nitrated polycyclic aromatic hydrocarbon (nitroPAH) is a potent mutagen which is reductively and/or oxidatively metabolized. Biological oxidation of nitroPAH, such as hydroxylation and epoxidation, is known, but chemical oxidation has been reported in only a few papers. NitroPAH is barely oxidized by various chemical oxidants because of the electron deficient property of the aromatic ring with the nitro substituent. Nucleophilic reactivity of superoxide anion radical is known, and thus the oxidation of nitroPAH with the chemically generated superoxide anion radical was carried out in this study. When 1-nitropyrene was reacted with KO2/18-crown-6 in dimethylformamide, 5-, 6-, 8-, and 9-hydroxy-1-nitropyrenes and 1-hydroxypyrene were obtained in preparative yields. Three isomeric dinitropyrenes, 3-nitrofluoranthene, 6-nitrobenzo[a]pyrene, and 6-nitrochrysene, were oxidized to hydroxy derivatives, some of which correspond to the oxidative metabolite of nitroPAH. The oxidation of dinitropyrenes with trifluoroperacetic acid gave K-region oxidized products.
硝化多环芳烃（nitroPAH）是一种强效诱变剂，可通过还原和/或氧化代谢。硝基多环芳烃的生物氧化，如羟基化和环氧化，是已知的，但化学氧化仅在少数几篇论文中有所报道。由于带有硝基取代基的芳香环具有缺电子特性，硝基多环芳烃几乎不被各种化学氧化剂氧化。超氧阴离子自由基的亲核反应性是已知的，因此本研究进行了用化学方法生成的超氧阴离子自由基对硝基多环芳烃的氧化反应。当1-硝基芘在二甲基甲酰胺中与KO₂/18-冠-6反应时，可制备得到5-、6-、8-和9-羟基-1-硝基芘以及1-羟基芘。三种异构体二硝基芘、3-硝基荧蒽、6-硝基苯并[a]芘和6-硝基 Chrysene被氧化为羟基衍生物，其中一些与硝基多环芳烃的氧化代谢产物相对应。用三氟过氧乙酸氧化二硝基芘得到K区域氧化产物。
