The fragmentation patterns of a novel series of dithiocarbamate derivatives with pharmaceutical activity were investigated by positive ion electrospray ionization mass spectrometry in conjunction with tandem mass spectrometry (ESI‐MSn). In the gas phase, the dithiocarbamate protonated molecules containing the piperazinium moiety undergo losses of bromide to form the piperazinium cation by ionization, followed by subsequent losses of methyl bromide, ring opening and rearrangement of piperazinium. Furthermore, the dithiocarbamate derivatives and their intermediates both undergo cleavage of the C–S bond to produce two common fragment ions. The different fragmentation observed for these compounds facilitated their identification and could be valuable in the further study of their metabolic pathways as prodrugs. Copyright © 2010 John Wiley & Sons, Ltd.