Synthesis and GC–MS analysis of a series of homologs and regioisomers of 3,4-methylenedioxypyrovalerone (MDPV)

A series of ten homologous and regioisomeric aminoketones related to the designer synthetic cathinone derivative MDPV were evaluated in this study. These compounds were prepared from a common precursor chemical, piperonal (3,4-methylenedioxybenzaldehyde). These aminoketones show major peaks in their mass spectra corresponding to the regioisomeric and homologous immonium cation fragments from the loss of the methylenedioxybenzoyl radical species. All ten compounds in this study show equivalent EI MS fragments for the 3,4-methylenedioxybenzoyl fragments (m/z 149) and the methylenedioxybenzene fragment at m/z 121. The m/z 149 results from ionization of the carbonyl oxygen followed by an alpha-cleavage fragmentation. The loss of CO from this ion yields the m/z 121 fragments common to all spectra. The regioisomeric aminoketones yield equivalent mass spectra including mass equivalent regioisomeric immonium cation base peaks. A subset of these compounds has the same molecular weight and almost identical mass spectra to that of the designer drug MDPV. An evaluation of the effects of homologation on gas chromatographic retention showed that addition of a methylene (CH2) in the nitrogen-containing ring increases retention more than the equivalent group added to the alkyl side-chain.