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Reactions of Esters of N-Hydroxy-2-acetamidophenanthrene with Cellular Nucleophiles and the Formation of Free Radicals upon Decomposition of N-Acetoxy-N-arylacetamides¹

Pacific Northwest Research Foundation, Seattle, Washington 98104

The sulfate ester of N-hydroxy-2-acetamidophenanthrene was prepared and was found to react significantly with methionine, adenosine, and guanosine. The adduct from the methionine reaction was characterized as 1-methylmercapto-2-acetamidophenanthrene. The levels of reaction with adenosine and guanosine were comparable, in contrast with the observation that N-acetoxy-2-acetamidofluorene shows a marked preference for guanosine as a substrate among the nucleosides. Although the level of reaction was lower, N-acetoxy-2-acetamidophenanthrene also reacted equally well with adenosine and guanosine. Molecular orbital calculations suggested that the previously studied adduct-forming abilities of N-acetoxy-N-arylacetamides might be related to their ability to form radical cations. On this basis, the abilities of these compounds to decolorize the stable free radical 2,2-diphenyl-1-picrylhydrazyl were tested. N-Acetoxy-2-acetamidofluorene rapidly decolorized 2,2-diphenyl-1-picrylhydrazyl in 20% ethanol at 45°, N-acetoxy-2-acetamidophenanthrene acted much more slowly, while N-acetoxy-4-acetamidobiphenyl and N-acetoxy-4-acetamidostilbene had almost negligible effects. These activities are closely related to the adduct-forming abilities of these compounds and may affect their carcinogenicities. We suggest that the chemistry of esters of N-hydroxy-2-acetamidophenanthrene shown here is typical of nonradical reactions of N-aryl-N-acetylnitrenium ions, while the reactivity of N-acetoxy-2-acetamidofluorene reflects a high percentage of radical cations among the ions formed upon decomposition of this ester.

¹ This is Paper 2 of the series, "N-Aryl-N-acetylnitrenium Ions in Aromatic Amine Carcinogenesis." Paper 1 is Ref. 26. This work was supported in part by Grant CA-13155-01, NIH, USPHS.

Received 11/16/72. Accepted 2/23/73.