GC-MS Studies on the Regioisomeric 2,3- and 3,4-Methylenedioxyphenethylamines Related to MDEA, MDMMA, and MBDB

Six regioisomeric methylenedioxyphenethylamines, including three known drugs of abuse (MDEA, MDMMA, MBDB) and their 2,3-methylenedioxy counterparts, have nearly identical mass spectra and cannot be distinguished by electron impact mass spectrometry alone. Differentiation requires derivatization to pentafluoropropionylamides (PFPA) or heptafluorobutrylamides (HFBA). Underivatized amines are not resolved on non-polar stationary phases but are separated on a more polar trifluoropropylmethyl polysiloxane (Rtx-200) or a permethylated beta-cyclodextran (Rtx-bDEX) column. The PFPA and HFBA derivatives of the 2,3-methylenedioxyphenethylamines elute before the corresponding 3,4-methylenedioxyphenethylamine derivatives on the Rtx-200 column.

Study at a glance

Abstract

Three regioisomeric 3,4-methylenedioxyphenethylamines having the same molecular weight and major mass spectral fragments of equal mass have been reported as drugs of abuse in forensic studies in recent years. These compounds are 3,4-methylenedioxy-N-ethylamphetamine (MDEA), 3,4-methylenedioxy-N-N-dimethylamphetamine (MDMMA), and N-methyl-1-(3,4-methylenedioxyphenyl)-2-butanamine (MBDB). The mass spectra of the regioisomers (2,3-methylenedioxyphenethylamines) are essentially equal to the three compounds reported as drugs of abuse. This paper reports the synthesis, mass spectral characterization, and chromatographic analysis of these six regioisomeric amines. The six regioisomeric methylenedioxyphenethylamines are synthesized from commercially available starting materials. The electron impact mass spectra of these regioisomers show some variation in the relative intensity of the major ions with only a couple of minor ions that may indicate side chain specific fragments. Differentiation by mass spectrometry is only possible after the formation of the perfluoroacyl derivatives, pentafluoropropionylamides (PFPA) and heptafluorobutrylamides (HFBA). Gas chromatographic separation on non-polar stationary phases (Rtx-1 and Rtx-5) is not successful at resolving the three 3,4-methylenedioxyphenethylamines from the three 2,3-methylenedioxyphenethylamines as the underivatized amines. The six underivatized amines are resolved on the more polar trifluoropropylmethyl polysiloxane Rtx-200 stationary phase as well as a permethylated beta-cyclodextran Rtx-bDEX stationary phase. Gas chromatographic separation is successful at resolving the four PFPA and the four HFBA derivatives on the Rtx-200 stationary phase as well as the permethylated beta-cyclodextran stationary phase. The 2,3-methylenedioxyphenethylamine derivatives (compounds 4 and 6) eluted before the 3,4-methylenedioxyphenethylamine derivatives (compounds 1 and 3) as both the PFPA and HFBA derivatives.