GAS-PHASE REACTIONS. 36. PYROLYSIS OF VINYL AZIDE.

Article abstract of DOI:10.1021/ja00364a037

The gas-phase pyrolyses of vinyl azide as well as of 1H-1,2,3-triazole have been investigated by means of PE spectroscopy. In accordance with predictions from MNDO hypersurface studies, vinyl azide in its lowest thermal decomposition channel splits off nitrogen to yield predominantly 2H-azirine as identified by the PE spectrum of the cool-trapped compound, which at higher temperatures rearranges to the most stable C//2H//3N isomer, acetonitrile. The experimental observations and the quantum chemical calculations both indicate that among those reaction pathways, which can readily be characterized by a suitably selected pair of reaction coordinates from the 12-dimensional hyperspace for the C//2H//3N moiety, synchronous nitrogen extrusion-azirine ring formation is the energetically most favorable one.