Abstract: | Radical cations derived from the ethers ROCH2CH2OR′ (R, R′ = H, CH3, C25) were studied, since β-distonic oxonium ions are often prepared from ionized ethers of glycol. The first step in the fragmentation is a 1,5-transfer of an α-hydrogen to oxygen of a terminal alkoxy group leading to a δ-distonic oxonium ion. This step is thermo-neutral and reversible in the ROCH2CH2OH radical cations and exothermic and irreversible in the dialkyl ether radical cations. Depending on R and R,′ these δ-distonic oxonium ions fragment by three reactions: the loss of an alcohol or a water molecule, the formation of a β-distonic oxonium ion ˙CH2CH2O(H)+R and a 1,4-H migration between carbon atoms. Competition between these processes is discussed. |