posted on 2024-01-24, 03:29authored byShivaiah Vaddypally, Alex N. Byrne, C. Franklin Goldsmith, Michael J. Zdilla, Vitaly G. Kiselev
Crystallization of the reaction mixture
of 2-amino-4,6-diazido-1,3,5-triazine
and excess tert-butylamine results in the isolation
of tert-butylammonium N,N-[1′H-(1,5′-bitetrazol)-5-yl]cyanamidate,
suggesting a complex decyclization/cyclization rearrangement involving
breakage of the six-membered aromatic ring and the formation of two
new five-membered azole rings mediated by deprotonation of the precursor
by the amine. The addition of tert-butylamine to
2-amino-4,6-diazido-1,3,5-triazine gives spectroscopic indication
of thermodynamically unfavorable reactivity in low-dielectric solvents,
and high-level quantum chemical computations also suggest
its formation to be unfavorable. A computed interconversion pathway
describes the likely reaction mechanism and supports the general thermodynamic
unfavorability of the reaction and the requirement for a high-dielectric
environment to template formation of the ionic product and its trapping
by crystallization.