The loss of CH3⋅ from some unsaturated dithioesters

Abstract The mechanism for the loss of CH 3 ⋅ (and C 2 H 5 ⋅) from the molecular ions of some unsaturated dithioesters of the type magnified image with n=0, 1, 2, has been studied. Based on first field free region metastable ion characteristics it is proposed that 1,3‐dithiolium type product ions are generated. Deuterium labelling experiments indicated that the molecular ions of the 2‐alkenyl alkanedithioates magnified image undergo a rearrangement prior to fragmentation which resembles the [3,3]sigmatropic rearrangement in solution chemistry.