The synthesis of potential metabolites of 1-nitropyrene, resulting from oxidation at the K-regions, is described. Reaction of 1-nitropyrene with OsO4 gave the cis-4, 5- and 9, 10-di-hydrodiols. These were separated and oxidized with activated MnO2 to give the corresponding 4, 5- and 9, 10-diones; further oxidation to the highly mutagenic lactones, 1- and 3-nitro-5H-phenanthro[4, 5-bed]pyran-5-one, was observed in these reactions. Reduction of the 4, 5-dione with KBH4 gave the trans-4, 5-dihydrodiol, which was identical to one of the metabolites of 1-nitropyrene. Reduction of the 9, 10-dione gave an unstable trans-9, 10-dihydrodiol, which was characterized as its diacetate. The u.v. spectra, n.m.r. spectra and h.p.l.c. retention times of these compounds are presented.
Bibliographical noteFunding Information:
National Science Foundation (PCM-7912083), the Camille and Henry Dreyfus Foundation and the Fleischmann Foundation. We especially are grateful to Dr A.Bencsath at Rockefeller University for assistance in obtaining the high resolution mass spectra. We wish to thank Ms. Gail Thiede for typing this manuscript. This research was supported by NCI Grant CA-35519. This is paper no. 90 in , 'A Study of Chemical Carcinogenesis'.