2-Nitro and 4-Nitro-iV-nitroso-N-ethylaniline: NMR Spectroscopy, Crystal Structures and Quantum Chemical Calculations

摘要

It is known that during the action of the propellant stabilizer Centralite I the decomposition products 2-nitro-N-nitroso-N-ethylaniline (1, R = Et) and 4-nitro-N-nitroso-N-ethyl-aniline (2) are formed. The multinuclear (~1H, ~(13)C and ~(14)N) NMR spectra of these aniline derivates reveal a dynamic behaviour involving rotation of the nitroso function as well as of the amino function. The H, C and N NMR data are reported and discussed in relation to the molecular geometry. The ~(14)N NMR data of three other 2-nitro-N-nitroso-N-alkylanilines (1, R = Me, n-Pr, nBu) have been determined also and are included for comparison. In addition the molecular and crystal structures of 1 (R = Et) and 2 are presented for the first time. We also report on quantum chemical calculations at the B3LYP level of theory using aug-cc-pVDZ basis sets. The energetically favoured configurations are presented and provide a better understanding of the analytical data.