%0 Journal Article
%T Fragmentation Pathways of Trifluoroacetyl Derivatives of Methamphetamine, Amphetamine, and Methylenedioxyphenylalkylamine Designer Drugs by Gas Chromatography/Mass Spectrometry
%A Takeshi Kumazawa
%A Kenji Hara
%A Chika Hasegawa
%A Seisaku Uchigasaki
%A Xiao-Pen Lee
%A Hiroshi Seno
%A Osamu Suzuki
%A Keizo Sato
%J International Journal of Spectroscopy
%D 2011
%I Hindawi Publishing Corporation
%R 10.1155/2011/318148
%X Methamphetamine (MA), amphetamine (AM), and the methylenedioxyphenylalkylamine designer drugs, such as 3,4-methylenedioxymethamphetamine (MDMA), 3,4-methylenedioxyethylamphetamine (MDEA), N-methyl-1-(3,4-methylenedioxyphenyl)-2-butanamine (MBDB), 3,4-methylenedioxyamphetamine (MDA), and 3,4-(methylenedioxyphenyl)-2-butanamine (BDB), are widely abused as psychedelics. In this paper, these compounds were derivatized with trifluoroacetic (TFA) anhydride and analyzed by gas chromatography/mass spectrometry using electron ionization in positive mode. Gas chromatographic separation for TFA derivatives of all compounds was successfully resolved using an Equity-5 fused silica capillary column with a poly (5% diphenyl-95% dimethylsiloxane) stationary phase. Base peaks or prominent peaks of MA, AM, MDMA, MDEA, MBDB, MDA, and BDB appeared at m/z 154, 140, 154, 168, 168, 135, and 135, respectively. These occurred due to ¦Á-cleavage from the amide nitrogen, splitting into the TFA imine species and benzyl or methylenedioxybenzyl cations. Further prominent fragment ions at m/z 118 for MA and AM, m/z 162 for MDMA, MDEA, and MDA, and m/z 176 for MBDB and BDB were produced by cleavage of the phenylpropane or methylenedioxypropane hydrocarbon radical cation via a hydrogen rearrangement. These fragmentation pathways for the TFA derivatives of all the compounds are summarized and illustrated in this paper. 1. Introduction In recent years, extensive attention in clinical and forensic toxicology has focused on the increasing abuse of methamphetamine (MA), amphetamine (AM), and methylenedioxyphenylalkylamine derivatives, such as 3,4-methylenedioxymethamphetamine (MDMA), 3,4-methylenedioxyethylamphetamine (MDEA), N-methyl-1-(3,4-methylenedioxyphenyl)-2-butanamine (MBDB), 3,4-methylenedioxyamphetamine (MDA), and 3,4-(methylenedioxyphenyl)-2-butanamine (BDB). A number of severe and even fatal intoxications attributable to these drugs have been reported [1¨C4]. Consequently, detection and identification analyses for these compounds are routinely performed in clinical and forensic laboratories. Several gas chromatographic methods to analyze MA, AM, MDMA, MDEA, MBDB, MDA, and BDB in doping control and toxicological analysis have been reported [5¨C8]. Because of their relatively low molecular weights, high polarity, and volatility, derivatization is necessary when using gas chromatography (GC) [9]. Acylation is one of the most popular derivatization reactions for primary and secondary amines and converts compounds into derivatives that are more easily separated or give an enhanced
%U http://www.hindawi.com/journals/ijs/2011/318148/