A new general route to N-alkoxybenzimidoyl azides [ArC(N3)=NOR] from a reaction of N-alkoxybenzimidoyl bromide [ArC(Br)=NOR] with sodium azide in DMSO is described. These reactions result in the Z-geometric configuration. These compounds show a moderate degree of thermal stability as assessed by differential scanning calorimetry, and lack reactivity in traditional 1,3-dipolar cycloaddition ‘click’ reactions. Upon exposure to electrophilic compounds (trifluoroacetic acid or acetyl chloride), these azide compounds can react by two pathways: a Schmidt-type rearrangement to form an N-alkoxyurea or an isomerization–cyclization reaction pathway to form an N-alkoxytetrazole. The route of the reaction has no dependence on solvent polarity and appears to depend upon the electrophile (H+vs. CH3CO+): reaction of the azide with trifluoroacetic acid results predominantly in the urea; reaction with acetyl chloride results solely in the tetrazole. Calculations indicate that the urea product is thermodynamically favored over the tetrazole product. They also indicate that both reaction conditions result in an equilibration between the starting azide and the tetrazole with the tetrazole being the major component in this equilibrium mixture. The fact that the azide also undergoes a Schmidt-type rearrangement to form an N-alkoxyurea when treated with trifluoroacetic acid appears to indicate that the barrier for aromatic ring migration is lower in the protonated azide produced on reaction with trifluoroacetic acid than in the acetylated azide produced on reaction with acetyl chloride. Copyright © 2009 John Wiley & Sons, Ltd.