Structure–activity relationship of nitrosating agents in the nitrosation reactions of ammonia: a theoretical study

Abstract

Nitrosating agents (NAs) stimulate the formation of powerful mutagenic and carcinogenic N-nitrosamines. As a model reaction, the nitrosation of ammonia by a series of NAs, i.e., HONO, N2O3, N2O4, ONOOH, ONCl, ONBr, ONSCN, ONOCH3, ONOC2H5, ONNC, ONOCl, and ONOSOCH3, was investigated at the CBS-QB3 level of theory. A structure–activity relationship of NAs in the nitrosation reactions of ammonia was established. The results indicate that the nitrosating reactivity of NAs (ON–X) has definite relationship with the heterolytic bond dissociation energies of ON–X and H–X, Mulliken charges of N and X atoms as well as number of the atoms in the ring of the transition state. In light of the established structure–reactivity relationship of NAs, ONNC was found to be a potential powerful nitrosating species.