RELATIVE STABILITIES OF NITRENIUM IONS DERIVED FROM POLYCYCLIC AROMATIC-AMINES - RELATIONSHIP TO MUTAGENICITY

The relative energetics of arylamine N-hydroxylation and N-O heterolysis (ArNH2 --> ArNHOH --> ArNH+) for condensed systems of two, three and four rings were calculated using semiempirical AM1 molecular orbital theory. The overall thermodynamics of N-hydroxylation were almost insensitive to the structure of the amine while differences in the energetics of nitrenium ion formation varied from 0 to 35 kcal mol-1. Limited correlations between the latter and the experimental TA98 and TA100 mutagenicities of the amines are presented.