Modeling the metabolic pathways of methylazoxymethanol: a semiempirical molecular orbital study.

The NDDO semiempirical molecular orbital method (Kikuchi, 1977; Kikuchi and Maeda, 1977) was used to model proposed nonenzymatic metabolic pathways for the decomposition of methazoxymethanol (MAM) to a methyldiazonium ion. It was found that the lowest transition path involved protonation of the azoxy oxygen atom to form a six-membered transition state structure which decomposes to the methyldiazonium ion, CH2O, and a hydroxyl ion. This metabolic pathway is consistent with models proposed by Druckrey and Lange (1972) and Miyadera (1975). The calculations also suggest that methylazoxyformaldehyde, an enzymatic product of MAM, may directly alkylate to nucleic acid base sites.