Chromatographic and spectroscopic methods of identification for the side-chain regioisomers of 3,4-methylenedioxyphenethylamines related to MDEA, MDMMA, and MBDB

Abstract

Three regioisomeric 3,4-methylenedioxyphenethylamines having the same molecular weight and major mass spectral fragments of equivalent mass have been reported as components of clandestine drug samples in recent years. These drugs of abuse are 3,4- methylenedioxy-N-ethylamphetamine, 3,4-methylenedioxy-N, N-dimethylamphetamine, and N-methyl-1-(3,4- methylenedioxyphenyl)-2-butanamine. These three compounds are a subset of a total of ten regioisomeric 3,4- methylenedioxyphenethylamines of molecular weight 207, yielding regioisomeric fragment ions of equivalent mass (m/z 72 and 135/136) in the electron impact mass spectrum. The specific identification of one of these compounds in a forensic drug sample depends upon the analyst's ability to eliminate the other regioisomers as possible interfering or coeluting substances. This paper reports the synthesis, mass spectral characterization, and chromatographic analysis of these ten unique regioisomers. The ten regioisomeric methylenedioxyphenethylamines are synthesized from commercially available precursor chemicals. The electron impact mass spectra of these regioisomers show some variation in the relative intensity of the major ions with only one or two minor ions that might be considered side-chain specific fragments. Thus, the ultimate identification of any one of these amines with the elimination of the other nine regioisomeric substances depends heavily upon chromatographic methods. Chromatographic separation of these ten uniquely regioisomeric amines is studied using gas chromatographic temperature program optimization.