The intrinsic reactivity of eight gaseous, mass-selected 2-azabutadienyl cations toward polar [4(+) + 2] cycloaddition with ethyl vinyl ether has been investigated by pentaquadrupole mass spectrometric experiments. Cycloaddition occurs readily for all the ions and, with the only exception of those from the N-acyl 2-azabutadienyl cations (N-acyliminium ions), the cycloadducts are found to dissociate readily upon collision activation (CID) both by retro-Diels-Alder reaction and by a characteristic loss of an ethanol (46u) neutral molecule. Ethanol loss from the intact polar [4(+) + 2] cycloadduct functions therefore as a structurally diagnostic test: 72 u neutral gain followed by 46 u neutral loss, i.e., as a combined ion-molecule reaction plus CID 'signature' for N-H, N-alkyl and N-aryl 2-azabutadienyl cations. The two N-acyliminium ions tested are exceptional as they form intact cycloadducts with ethyl vinyl ether which dissociate exclusively by the retro-Diels-Alder pathway. Copyright (C) 2003 John Wiley Sons, Ltd.381010751080