SOFT 2004 Meeting Abstracts - Society of Forensic Toxicologists

F25
IDENTIFICATION OF CHLORINATED 3,4-METHYLENEDIOXYMETHAMPHETAMINE
IN ILLICIT DRUG ABUSER URINE
4
Vera Maresova 1 ', Jan Hamplt, Zdenek Chundela 2 , Frantisek Zrcek 3 , Miroslav Pohgek , Jiff Chadt'
'Institute of Forensic Medicine and Toxicology, 1 st Medical Faculty and Hospital, Charles University of
Prague; 2 Department of Doping Control, General Faculty Hospital, Prague, 3 Institute of Criminalistics,
Prague, 4 J. Heyrovsky Institute of Physical Chemistry, Prague, Czech Republic
Aim: The aim of this study was to identify 3,4-methylenedioxymethamphetamine (MDMA, Ecstasy) and
chlorinated 3,4-methylenedioxymethamphetamine (CI-MDMA) using combined thin layer chromatography
(TLC) and gas chromatography-mass spectrometry (GC-MS). The compound was identified jointly with MDMA
in illicit drug abuser urine. The urine specimen has yielded positive EMIT immunoassay screenings for
cannabinoides, amphetamines and cocaine. GC-MS confirmation of amphetamines has revealed the presence of
amphetamine, methamphetamine, ephedrine, norephedrine, 3,4-methylenedioxymethamphetamine and 3,4­
methylenedioxyamphetamine (MDA).
Methods: Thin layer chromatography: In the basic extract a routine analysis of urine by TLC for amphetamines
using fractional diethylether liquid/liquid extraction identified ephedrine, the major component MDMA and an
unknown compound. In the TLC system our unknown compound behaved differently than the MDMA. The TLC
plate with silica stationary phase was used (Merck), eluent ethylacetate ethanol ammonia (36:2:2). Gas
chromatography-mass spectrometry: The unknown compound isolated by TLC technique was analysed by
positive chemical ionization (PCI). The base peak mlz 228 (MH+) exhibited a characteristic A+2 isotopic cluster
indicating the presence of a monochloro-substituted compound. The molecular ion of CI-MDMA was found at
227 mlz. The MS spectrum of the unknown compound in electron ionization (EI) exhibited characteristic A+2
chlorine isotopic cluster typical for ion at mlz 169 (mlz 135-1+35) and for molecular ion at mlz 227 (mlz 193­
1+35). To confirm CI-MDMA structure, the unknown compound isolated by TLC technique was acetylated,
trifluoroacetylated, silylated, heptafluorobutyrylated and analyzed by GC-MS. The EI-MS spectra ofMDMA and
CI-MDMA after derivatization exhibited structural similarities. The EI-MS spectrum of MDMA contained ions
193, 177, 135, 77, 58 [I]. The EI-MS spectra of derivatized CI-MDMA exhibited characteristic A +2 isotopic
cluster for ion at mlz 169 (mlz 135 -I +35) for all used derivatization methods mentioned above. Another
isotopic A + 2 cluster was created in all molecular ions of each derivatized chlorinated MDMA: acetylated CI­
MDMA had molecular ion at mlz 269 (mlz 227 - I + 43), silylated CI-MDMA had molecular ion at mlz 299 (mlz
227 - I +73), trifluoroacetylated CI-MDMA had molecular ion at mlz 323 (mlz 227 I + 97),
heptafluorobutyrylated CI-MDMA had molecular ion at mlz 423 (mlz 227 - I + 197). Next joint cluster at mlz 196
(162 - I + 35) occurred in acetylated, trifluoroacetylated and heptafluorobutyrylated derivates with the exception
of silylated derivates. GC-MS analysis were performed using Hewlett Packard 5890 Gas Chromatograph with
5890 autosampler coupled to a Hewlett Packard 5972 MS detector and Finnigan MAT Magnum. CI-GC-MS
Finnigan MAT Magnum conditions were as follows: ionization gas methanol vapour, ionization energy of
electrons 70 eV, specific conditions for ion trap CIIMCI parameters: CI maximum ionization time 1500 IlSec, CI
maximum reaction time 100 msec, CI ionizatin storage level 82 dacs, CI reaction storage level 164 dacs, reagent
ion ejection level 85 amu, MCI ionization time 100 Ilsec, reagent ion ejection adjust 100 %, reagent reaction time
54001lsec.
Conclusion: A chlorinated MDMA was identified after derivatization of unknown compound isolated by TLC
technique. With using literature source [2] and interpretation our mass spectra of heptafluorobutyrylated CI­
MDMA we can declare that unknown compound should be 6-CI-MDMA. 6-CI-MDMA is listed in New
synthetic drugs reported in Europe and the USA since the mid-1990s in joint action of The European Monitoring
Centre for Drugs and Drug Addiction (EMCDDA)[3].
Acknowledgment: The work has been supported by the project ofMSMNo. 111100005.
l. H. H. Maurer, A. Weber, K. Pfleger: Mass Spectra and GC data of Drugs, Poisons, Pesticides, Pollutants
and their metabolites, 1-4, VCH Verlagsgesellschaft, Weinheim, Germany, 1992
2. R.l Lewis, D. Reed, A. G. Service, A. M. Langford: J. Forensic. Sci. 2000; 45(5): 1119-1125
3. L. A. King, A. J. Poortman van der-Meer: Sci. & Just. 2001, 41(3): 200-202
Keywords: chlorinated MDMA, GC-MS analysis
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