The pyrrolizidine alkaloids in Senecio jacobaea can be hydrolyzed to the common base, retronecine, and derivatized to form the bistrifluoroacetate, bisheptafluorobutyrate, diacetate and bistrimethylsilyl ether. The analysis of the fluorinated compounds by electron capture provides sensitivity for detection of these alkaloids. The bond weakening effect in the ion formed on electron impact, between the allylic carbon and alkyl ester oxygen due to the electron withdrawing fluorinated groups of the ester, changes the driving force for fragmentation from the nitrogen alpha-cleavage reaction to a charge site migration. This yields alkyl-oxygen bond cleavage and formation of a stabilized allylic cation which is the base peak.