Ab initio calculations of the electronic structures of Dimethylnitrosamine (DMN) and its Metabolite Hydroxydimethylnitrosamine (HDMN): A possible intermediate in carcinogenesis by DMN

Abstract

The structure of N,N'-dimethylnitrosamine (DMN) and its a-hydroxy derivative have been computed using the ab initio force method with a 4-21 basis set. The results are compared with experiment for DMN.

Ab initio calculations relevant to the mechanism of chemical carcinogenesis byN-nitrosamines. I. The nitrosation of amines

“…The above scheme has implications with respect to the nitrosation of tertiary amines, and the fact that calculations for the reaction (9) (CH3),N + NO' -(CH3),NN0 + CH; (AE = +96 kJ mol-I) (9) show that this process has a low positive value of AE, indicate that this process might well be favored when hydration is taken into account. Using the following hydration scheme:…”

“…The mechanism of the formation of the N-nitrosamines is also not fully understood; in particular, the nature of the nitrosating species has been the subject of considerable debate [7]. In an attempt to clarify the mechanisms involved, we initiated a project several years ago whose goal was the understanding of the mechanism of the formation and decomposition of DMN, in which we use the methods of quantum chemistry to investigate the potential energy surfaces for the relevant reactions [8,9]. In this article, we examine the energetics of the nitrosation of amines and the production of DMN.…”