Synthesis and Characterization of Novel Bis-Triazenes: 3,8-Di[2-aryl-1-azenyl]-1,3,6,8-tetraazabicyclo[4.4.1]undecanes and 1,3-Di-2-[(4-methoxyphenyl)-1-diazenyl]imidazolidine. The Reaction of Diazonium Ions with Ethylenediamine/Formaldehyde Mixtures.
Reaction of a diazonium salt solution with a mixture of ethylenediamine and an excess of formaldehyde or 1,3,6,8-tetraazatricyclo[4.4.1.1(3,8)]dodecane results in the formation of a novel class of bis-triazenes, the 3,8-di(2-aryl-1-azenyl)-1,3,6,8-tetraazabicyclo[4.4.1]undecanes (6), which have been fully characterized by spectroscopy, elemental analysis, and X-ray crystallography. The X-ray data show that the tetraazabicyclic cage is folded back so that the aryl groups interact by pi-pi-stacking. The proton NMR spectra are made complex by the presence of three sets of distinctly different diastereotopic methylene groups, which have been assigned by a combination of decoupling and 2D-NMR experiments. In the case involving coupling of the p-anisidine diazonium derivative to ethylenediamine and formaldehyde mixtures, 1,3-di-2-[(4-methoxyphenyl)-1-diazenyl]imidazolidine (8) was the only product isolated. Its structure has been assigned on the basis of (1)H and (13)C NMR spectra and X-ray crystallography.
Peori
M. Brad
MB
Department of Chemistry, Dalhousie University, Halifax, Nova Scotia, Canada B3H 4J3.
Vaughan
Keith
K
Hooper
Donald L.
DL