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International Journal of Spectroscopy


Volume 2011, Article ID 318148, 12 pages
doi:10.1155/2011/318148

Research Article
Fragmentation Pathways of Trifluoroacetyl Derivatives of
Methamphetamine, Amphetamine, and
Methylenedioxyphenylalkylamine Designer Drugs by
Gas Chromatography/Mass Spectrometry

Takeshi Kumazawa,1 Kenji Hara,2 Chika Hasegawa,3 Seisaku Uchigasaki,4


Xiao-Pen Lee,1 Hiroshi Seno,5 Osamu Suzuki,6 and Keizo Sato1
1 Department of Legal Medicine, Showa University School of Medicine, 1-5-8 Hatanodai, Shinagawa-ku, Tokyo 142-8555, Japan
2 Department of Forensic Medicine, Fukuoka University School of Medicine, 7-45-1 Nanakuma, Jonan-ku, Fukuoka 814-0180, Japan
3 Department of Legal Medicine, Toho University School of Medicine, 5-21-16 Omorinishi, Ota-ku, Tokyo 143-8540, Japan
4 Department of Legal Medicine, Nihon University School of Medicine, 30-1 Ohyaguchi-kamicho, Itabashi-ku, Tokyo 173-8610, Japan
5 Department of Legal Medicine, Aichi Medical University School of Medicine, Nagakute-cho, Aichi 480-1195, Japan
6 Department of Legal Medicine, Hamamatsu University School of Medicine, 1-20-1 Handayama, Higashi-ku,

Hamamatsu 431-3192, Japan

Correspondence should be addressed to Takeshi Kumazawa, kumazawa@med.showa-u.ac.jp

Received 24 February 2011; Accepted 26 June 2011

Academic Editor: Stefan Schmatz

Copyright © 2011 Takeshi Kumazawa et al. This is an open access article distributed under the Creative Commons Attribution
License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly
cited.

Methamphetamine (MA), amphetamine (AM), and the methylenedioxyphenylalkylamine designer drugs, such as 3,4-methylene-
dioxymethamphetamine (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 α-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 (BDB). A number of severe and even fatal intoxications


attributable to these drugs have been reported [1–4].
In recent years, extensive attention in clinical and forensic Consequently, detection and identification analyses for these
toxicology has focused on the increasing abuse of metham-
compounds are routinely performed in clinical and forensic
phetamine (MA), amphetamine (AM), and methylenedioxy-
laboratories.
phenylalkylamine derivatives, such as 3,4-methylenedioxym-
ethamphetamine (MDMA), 3,4-methylenedioxyethylamph- Several gas chromatographic methods to analyze MA,
etamine (MDEA), N-methyl-1-(3,4-methylenedioxyphenyl) AM, MDMA, MDEA, MBDB, MDA, and BDB in doping
-2-butanamine (MBDB), 3,4-methylenedioxyamphetamine control and toxicological analysis have been reported [5–
(MDA), and 3,4-(methylenedioxyphenyl)-2-butanamine 8]. Because of their relatively low molecular weights, high
2 International Journal of Spectroscopy

×107
TIC (1) (2)
2 (3) (4) (5) (6)(7)

0
2

m/z 91
0
2

m/z 110
0
2

m/z 118
0
2

m/z 135
Intensity

0
2

m/z 140
0
2

m/z 154
0
2

m/z 162
0
2

m/z 168
0
2

m/z 176
0
4 4.5 5 5.5 6 6.5 7 7.5 8 8.5 9 9.5 10
(min)

Figure 1: Mass chromatograms obtained from GC/MS analysis using Equity-5 capillary column for TFA derivatives of seven analytes. The
ionizing energy was 70 eV with an emission current of 60 μA. Ten nanograms of each analyte were injected in the positive-ion EI mode.
Peaks: (1) AM-TFA; (2) MA-TFA; (3) MDA-TFA; (4) BDB-TFA; (5) MDMA-TFA; (6) MDEA-TFA; and (7) MBDB-TFA.

polarity, and volatility, derivatization is necessary when using MDMA, MDEA, MBDB, MDA, and BDB using GC/MS in EI
gas chromatography (GC) [9]. Acylation is one of the most mode after acylation derivatization.
popular derivatization reactions for primary and secondary
amines and converts compounds into derivatives that are 2. Experimental Part
more easily separated or give an enhanced response in
GC compared with the parent compound [10]. GC/mass 2.1. Materials. Hydrochloride salts of MDA, BDB, MDMA,
spectrometry (MS) using the electron ionization (EI) mode and MBDB were prepared as described briefly here. MDA
is a widely used technique in drug analysis, as it leads to and BDB syntheses were performed according to the proce-
a number of fragment ions providing structural information dures described by Lindeke and Cho [20]. MDA was synthe-
[11]. Although quantitative analysis of MA, AM, and the sized by hydrogenation of 1-(3,4-methylenedioxyphenyl)-2-
methylenedioxyphenylalkylamine designer drugs has been nitropropene, which was prepared beforehand by condensa-
frequently performed in clinical and forensic toxicology by tion of piperonal and nitroethane. BDB was synthesized by
GC/MS-EI with derivatization [8, 12–17], systematic studies hydrogenation of 1-(3,4-methylenephenyl)-2-nitrobutene,
of mass spectrometric behavior for these compounds have which was prepared beforehand by condensation of piper-
been limited [9, 18, 19]. In this paper, we present mass onal and nitropropane. MDMA and MBDB syntheses
spectra and detailed fragmentation pathways for MA, AM, were performed according to the procedures described by
International Journal of Spectroscopy 3

70 eV 154 MA-TFA MW 245


100 CH3
75 N CF3

50 CH3 O
110 118
Relative abundance (%)

25 91 M+•
65 69
245
0

100 20 eV 154

75

50 118

25 110 M+•
245
0
50 75 100 125 150 175 200 225 250 275 300 325 350
(m/z)
+•
CH3

N CF3 m/z 245

CH3 O
CH 3 EI EI CH3

N CF3 EI N CF3

CH3 O+• CH3 +•


H O
N+• CF3
α-cleavage
−CF3 • O
CH3 H-rearrangement
CH3

N α-cleavage CH3
CH2 •
N CF3
CH3 O+
CH3 +
−CO CH2 • OH
CH3 N+ CF3
N+ CH3
CH3 O m/z 154
N + CF3
CH3 C
CH3 CH2 • OH
H3 C + CF3 CH3
N N
N CF3
CH3 O
H3 C OH
CH2 +
H3 C C O
H CH+
+
m/z 91 H3 C N C CF3 CH2 •
m/z 110 m/z 118
+

m/z 91
−C2 H2
+

m/z 65

Figure 2: EI mass spectra of the TFA derivative of MA and their probable fragmentation pathway.
4 International Journal of Spectroscopy

70 eV 140 AM-TFA MW 231


100 118 H

75 N CF3

50 CH3 O
91
Relative abundance (%)

25 69 M+•
65
231
0

20 eV 118
100

75
140
50

25 91 M+•
231
0
50 75 100 125 150 175 200 225 250 275 300 325 350
(m/z)
+•
H
CF3 m/z 231
N

H CH3 O
EI EI H
N CF3 N CF3
EI
CH3 O+• H O+•
H
N+• CF3
α-cleavage
−CF3 • CH3 O
H-rearrangement
H
N α-cleavage
H
CH2 •
CH3 O+ N CF3
−CO
H H CH2 • OH+
N+ N+ CF3
H
CH3 CH3 O m/z 140 N + CF3
H C
N CH2 • OH
H
CH3 N CF3
CH2 + OH
m/z 91
CH+
CH2 •
+
m/z 118
m/z 91
−C2 H2
+

m/z 65

Figure 3: EI mass spectra of the TFA derivative of AM and their probable fragmentation pathway.
International Journal of Spectroscopy 5

70 eV 154 MDMA-TFA MW 289


100 CH3
162
N CF3
75 O
135
CH3 O
50 110 O
Relative abundance (%)

25 51
77 M+•
69 289
0

20 eV 162
100

75 154

50
M+•
25 135 289
110
0
50 75 100 125 150 175 200 225 250 275 300 325 350
(m/z)

CH3 +•

O N CF3 m/z 289

CH3 O
O
CH 3 EI EI CH3
O N CF3
EI O N CF3
CH3 O+•
O CH3 O+•
O H
O N+• CF3
α-cleavage CH3 O
O
−CF3 • H-rearrangement
CH3
CH3
N α-cleavage
O •
O CH2 N CF3
O
O CH3 O+ O +
O CH2 • OH
CH3
−CO
CH3 N+ CF3 CH3
N+ CH3 O m/z 154 O N + CF3
O C

O CH3 O CH2 • OH
CH3
CH3 H3 C + N CF3
CF3
N N
OH
O
CH3 H3 C O
CH+
O CH2 + CH2 •
H3 C C O O
H
O + m/z 162
H3 C N C CF3
m/z 135
m/z 110

Figure 4: EI mass spectra of the TFA derivative of MDMA and their probable fragmentation pathway.
6 International Journal of Spectroscopy

70 eV 168 MDEA-TFA MW 303


100
C2 H5
75 162 CF3
O N
140
50 CH3 O
135 O
Relative abundance (%)

69 124
25 51 77 M+•
303
0
162
100 20 eV 168

75

50

25 140 M+•
124 135 303
0
50 75 100 125 150 175 200 225 250 275 300 325 350
(m/z)
C2 H5 +•

O N CF3 m/z 303

CH3 O
O
C2 H 5 EI EI C2 H5
O N CF3
EI O N CF3
CH3 O+•
O C2 H5 O+•
O H
O N+• CF3
α-cleavage CH3 O
O
−CF3 • H-rearrangement
C2 H 5
C2 H5
N α-cleavage
O •
O CH2 N CF3
O
O CH3 O+ O +
O CH2 • OH
C2 H5
−CO
C2 H 5 N+ CF3 C2 H5
N+ CH3 O m/z 168 O N + CF3
O C
−C2 H4 CH2 • OH
O CH3 C2 H5 O
H C2 H5
C2 H5 N+ CF3
N CF3
N+ CF3
N OH
CH3 O
CH3 O
CH3 O
C2 H5 m/z 140 CH+
+ CF3
O CH2 + N CH2 •
O
O O m/z 162
m/z 135 H3 C

H3 C C O
H
+
C2 H5 N C CF3
m/z 124

Figure 5: EI mass spectra of the TFA derivative of MDEA and their probable fragmentation pathway.
International Journal of Spectroscopy 7

70 eV 168 MBDB-TFA MW 303


100
CH3
75 176 N CF3
O
135 C2 H5 O
50 O
110
Relative abundance (%)

69
25 51 77 M+•
303
0
176
100 20 eV
168
75

50
M+•
25 135
110 303
0
50 75 100 125 150 175 200 225 250 275 300 325 350
(m/z)
CH3 +•
m/z 303
O N CF3

C2 H5 O
O
CH 3 EI EI CH3
O N CF3
EI O N CF3
C2 H5 O+•
O CH3 O+•
O
O N+• CF3 H
α-cleavage C2 H5 O
O
−CF3 • H-rearrangement
CH3
CH3
N α-cleavage
O
O CH2 • N CF3
O
O C2 H5 O+ O +
OH
O CH2 •
CH3
−CO
CH3 N+ CF3 CH3
N+ O N + CF3
O C2 H5 O m/z 168 C
OH
O C2 H5 O CH2 •

CH3 H3 C CH3
+ CF3
N N CF3
N
OH
O
C2 H5 C2 H5 O
CH+
O CH2 +
C2 H5 C O O CH2 •
H
O +
C m/z 176
H3 C N CF3
m/z 135
m/z 110

Figure 6: EI mass spectra of the TFA derivative of MBDB and their probable fragmentation pathway.
8 International Journal of Spectroscopy

135 MDA-TFA MW 275


100 70 eV H
N CF3
75 O
CH3 O
50 162 O

M+•
Relative abundance (%)

25 77
51 140 275
69
0

135 162
100 20 eV

75 M+•
275
50

25
140
0
50 75 100 125 150 175 200 225 250 275 300 325 350
(m/z)
H +•

N CF3 m/z 275


O
CH3 O
O
H EI EI H
O N CF3
EI O N CF3
CH3 O+•
O H O+•
O H
O N+• CF3
α-cleavage CH3 O
O
−CF3 • H-rearrangement
H
H
N α-cleavage
O
O CH2 • N CF3
O
O CH3 O+ O +
O CH2 • OH
H
−CO
N+ CF3 H
H
N+ CH3 O O N + CF3
O C
m/z 140
CH2 • OH
O CH3 O
H
H N CF3
N OH

CH3 O
CH+
CH2 +
O O CH2 •

O m/z 162
m/z 135

Figure 7: EI mass spectra of the TFA derivative of MDA and their probable fragmentation pathway.

Repke et al. [21]. MDMA and MBDB were prepared by MDEA hydrochloride was synthesized according to pub-
hydrogenation of MDA and BDB, respectively, followed lished procedures [22] that follow. Briefly, acetic anhydride
by benzyloxycarbonylation with benzyloxycarbonyl chloride. was added to a solution of MDA free base in pyridine and
These four compounds, MDA, BDB, MDMA, and MBDB, the mixture was stirred at room temperature for 0.5 h. The
were then finally converted to their hydrochloride salts. reaction was quenched by addition of distilled water and
International Journal of Spectroscopy 9

70 eV 135 BDB-TFA MW 289


100
H
75 N CF3
O
50 C2 H5 O
176 O
Relative abundance (%)

25 77 M+•
51 154 289
69
0
135
100 20 eV 176

75
M+•
50 289

25
154
0
50 75 100 125 150 175 200 225 250 275 300 325 350
(m/z)

H +•

O N CF3 m/z 289

C2 H5 O
O
H EI EI H

O N CF3 N CF3
EI O
C2 H5 O+•
O H O+•
O
O N +• CF3 H
α-cleavage C2 H5 O
O H-rearrangement
−CF3 •
H
H
N α-cleavage
O N CF3
O CH2 • O
O C2 H5 O+ O +
OH
O CH2 •
H
−CO
H N+ CF3 H

N+ O N + CF3
O C2 H5 O m/z 154 C

O CH2 • OH
O C2 H5
H
H
N CF3
N
OH
C2 H5 O
CH+
CH2 +
O O CH2 •
m/z 176
O
m/z 135

Figure 8: EI mass spectra of the TFA derivative of BDB and their probable fragmentation pathway.

acidified with hydrochloric acid. The aqueous mixture was a solution of acetic anhydride and pyridine. The resulting
extracted with diethyl ether and the organic phase was solution of N-acetyl-3,4-methylenedioxyamphetamine was
evaporated to dryness in vacuo. The residue, N-acetyl-3,4- added to lithium aluminum hydride in anhydrous tetrahy-
methylenedioxyamphetamine, was recrystallized from ethyl drofuran and the reaction mixture was heated at reflux for
acetate/hexane, and the crystalline product was added to three days. After cooling the reaction mixture on an ice-bath,
10 International Journal of Spectroscopy

the excess hydride was decomposed by addition of distilled as follows: initial temperature, 60◦ C for 1 min; from 60
water then sodium hydroxide. The mixture was filtered and to 200◦ C at 20◦ C min−1 ; finally from 200 to 300◦ C at
the solvent removed in vacuo. The residue was dissolved in 40◦ C min−1 . The mass spectrometer was operated in the
ethyl alcohol and concentrated hydrochloric acid was added. positive-ion EI mode using ionizing energy of 70 eV and
This aqueous solution was extracted with ethanol/diethyl emission current of 60 μA, or ionizing energy of 20 eV and
ether followed by diethyl ether, and the solvent removed emission current of 10 μA. Full-scan data were obtained with
in vacuo. Recrystallization of the residue gave MDEA mass range of m/z 50–350, scan interval of 0.5 s, and scan
hydrochloride. speed of 769 amu/s.
AM sulfate was synthesized according to the literature
procedure [20]. All the compounds described above were 3. Results and Discussion
prepared at the Department of Forensic Medicine, Fukuoka
University School of Medicine. The salts were pure and TFA anhydride is the most widely used derivatizing agent,
characterized by mass spectrometry. MA hydrochloride was known to react with and acylate the primary and secondary
purchased from Dainippon Pharmaceutical Co., Ltd. (Osaka, amine groups of the amphetamine-type illicit drugs [8, 10,
Japan). Trifluoroacetic (TFA) anhydride was obtained from 12, 15–17, 23]. However, excess TFA and byproducts such as,
Pierce (Rockford, Ill, USA). Other chemicals used were of the trifluoroacetic acid, are produced in reactions with the target
highest purity commercially available. compounds [24]. These have to be removed from the extract
prior to the GC/MS analysis, in order to avoid damaging to
2.2. Preparation of Standard Solutions. Stock standard solu- the GC column [25]. In the present study, our sample prepa-
tions of MA, AM, MDMA, MDEA, MBDB, MDA, and BDB ration of drying the reaction mixture with TFA anhydride
were prepared separately by dissolving an accurately weighed under a stream of nitrogen and reconstituting the residue in
amount of each compound in methanol to achieve a con- ethyl acetate greatly reduced both excess derivatizing agent
centration of 1 mg mL−1 . All stock solutions were stored at and the acid byproduct. The TFA derivatives of the seven
4◦ C. Working standard solutions from 1–5 μg 10 μL−1 in compounds were well separated with good peak shapes and
methanol were prepared by serial dilution from the stock no remarkable impurities within 9.5 min (Figure 1). In the
standard solutions. Ten microliter working standard solu- preliminary experiment, the mixtures of MA, AM, MDMA,
tions were evaporated to dryness under a gentle stream of MDEA, MBDB, MDA, and BDB were compared on different
nitrogen and the residue was used for derivatization. stationary phases using several temperature programs. The
best compromise between analysis time and resolution was
2.3. Derivatization. MA, AM, MDMA, MDEA, MBDB, achieved on the Equity-5 capillary column.
MDA, and BDB were derivatized with TFA anhydride. Figures 2–8 show the EI full-scan mass spectra with ion-
A 100 μL aliquot of TFA anhydride/ethyl acetate (5 : 1, v/v) izing energies of 70 eV and 20 eV for the TFA derivatives of
was added to each residue, and samples were capped, mixed, MA, AM, MDMA, MDEA, MBDB, MDA, and BDB and their
and heated at 80◦ C for 10 min with an aluminum block probable fragmentation pathways. The molecular ions for
heater (Reacti-Therm Heating/Stirring Model; Pierce). After MA and AM were barely detectable and therefore of little
cooling to room temperature, the solvent was then evapo- quantitative value, at m/z 245 and m/z 231, respectively,
rated to dryness under a stream of nitrogen, and residues (Figures 2 and 3). MDMA, MDEA, MBDB, MDA, and BDB
were reconstituted in 50 μL ethyl acetate. A 1 μL aliquot of produced molecular ions with relatively high abundance (6–
sample solution was submitted for GC/MS analysis. 12% at 70 eV and 9–53% at 20 eV) at m/z 289, 303, 303, 275,
and 289, respectively (Figures 4–8). The relative abundance
2.4. GC/MS Conditions. All analyses were performed using of molecular ions in the EI mass spectra of these derivatives
a Shimadzu GC-2010 gas chromatograph interfaced with may depend substantially on the chemical nature of sub-
a Shimadzu QP-2010 quadrupole mass spectrometer (Shi- stituents directly attached to the benzene ring, such as their
madzu Corp., Kyoto, Japan). The GC/MS was operated with inductive effect and/or their thermal stability.
an interface temperature of 300◦ C and an ionization source MA and AM produced prominent peaks at m/z 154 and
temperature of 250◦ C. The mass spectrometer was tuned 140, respectively, in the mass spectra (Figures 2 and 3). These
daily, using perfluorotributylamine. A solvent delay of ions were the TFA imine species, probably by α-cleavage of
4.0 min was set to protect the filament from oxidation. Chro- the amide nitrogen of their parent molecules. This cleavage
matographic separation was achieved using an Equity-5 could also simultaneously lead to benzyl cation ([C7 H7 ]+ )
fused silica capillary column (30 m × 0.32 mm i.d., 0.25 μm fragment at m/z 91. The mass spectra for both derivatives
film thickness, poly(5% diphenyl-95% dimethylsiloxane) showed high relative abundance ions at m/z 118 (35–44%
stationary phase; Supelco, Bellefonte, Pa, USA). Helium, for MA and 97–100% for AM), corresponding to the phenyl-
with a minimum purity of 99.99995%, was used as carrier propane hydrocarbon radical cation (Figures 2 and 3). The
gas at a constant pressure of 42.3 kPa (initial flow rate of formation of this cation can be explained by a hydrogen
2 mL min−1 ). The gas chromatograph was equipped with rearrangement [26]. This involves migration of a γ-hydrogen
a split/splitless injection port, operated at 250◦ C. Samples atom from the alkyl group to the carbonyl oxygen through
were injected in the splitless mode, at a column temperature a cyclic six-membered transition state, followed by cleavage
of 60◦ C, and the splitter was then opened after 1 min. The of the alkyl carbon-nitrogen bond in the side chain leading
gas chromatograph oven temperature was programmed to the loss of imine species.
International Journal of Spectroscopy 11

For MDMA, MDEA, and MBDB, prominent peaks at m/z 154 or m/z 168 prominent peak ions. These characteristic
154 (for MDMA) and 168 (for MDEA and MBDB) and the fragmentation patterns of TFA derivatives of MA, AM, and
3,4-methylenedioxybenzyl cation peak at m/z 135 probably the methylenedioxyphenylalkylamine designer drugs will aid
resulted from α-cleavage of the amide nitrogen (Figures 4–6). in the identification of these drugs from biological samples
MDA and BDB both have H as a substituent on the nitrogen in clinical and forensic toxicology.
atom and both gave base peak ions at m/z 135 corresponding
to the 3,4-methylenedioxybenzyl cation (Figures 7 and 8), Acknowledgment
produced via α-cleavage of the amide of their parent mole-
cules. The spectra of these methylenedioxy derivatives This study was supported in part by a Grant-in-Aid for sci-
showed characteristic fragment ions at m/z 162 for MDMA, entific research (C) from the Japan Society for the Promotion
MDEA, and MDA and m/z 176 for MBDB and BDB, with of Science (JSPS).
high relative abundance of 33–97% at 70 eV and 94–100%
at 20 eV. Both of these fragment ions can be assigned References
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The compounds with a methyl substituent on the nitro- (MDMA) and Eve (MDEA) misuse: an immunohistochemical
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104, no. 1, pp. 65–74, 1999.
cation ([CH3 –N≡C–CF3 ]+ ) at m/z 110 (Figures 2, 4, and 6).
[2] N. Carter, G. N. Rutty, C. M. Milroy, and A. R. W. Forrest,
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produced analogous cation at m/z 124 corresponding to of Legal Medicine, vol. 113, no. 3, pp. 168–170, 2000.
([C2 H5 –N≡C–CF3 ]+ ), with low relative abundance of 4% [3] R. Garcı́a-Repetto, E. Moreno, T. Soriano, C. Jurado, M. P.
at 20 eV and 7% at 70 eV (Figure 5). We propose that this Giménez, and M. Menéndez, “Tissue concentrations of
resulted from the decomposition reaction of the four-mem- MDMA and its metabolite MDA in three fatal cases of over-
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fragmentation process of the m/z 154 or 168 cations 114, 2003.
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pp. 478–485, 2009.
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[5] P. R. Paetsch, G. B. Baker, L. E. Caffaro, A. J. Greenshaw,
of the m/z 168 cation to lose ethylene (C2 H4 ). These results G. A. Rauw, and R. T. Coutts, “Electron-capture gas chro-
were consistent with the previous report [27]. matographic procedure for simultaneous determination of
Benzyl or tropylium cation at m/z 91 produced in MA amphetamine and N-methylamphetamine,” Journal of Chro-
and AM occurred due to a neutral loss of acetylene (C2 H2 ), matography, vol. 573, no. 2, pp. 313–317, 1992.
which gave rise to the cyclopentadienyl ion ([C5 H5 ]+ ) at m/z [6] P. Marquet, E. Lacassie, C. Battu, H. Faubert, and G. Lachâtre,
65 (Figures 2 and 3). Thus, m/z 91/65 for MA and AM was “Simultaneous determination of amphetamine and its analogs
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although these ions are less favored in the mass spectra. The trometry,” Journal of Chromatography B, vol. 700, no. 1-2, pp.
spectra for MDA and BDB showed complementary ions at 77–82, 1997.
m/z 140 and m/z 154, respectively, with relative abundance [7] F. T. Peters, S. Schaefer, R. F. Staack, T. Kraemer, and H.
of 7% at 70 eV and 9–11% at 20 eV, corresponding to the H. Maurer, “Screening for and validated quantification of
amphetamines and of amphetamine- and piperazine-derived
TFA imine species. The ion of m/z 69 ([CF3 ]+ ) with 4–
designer drugs in human blood plasma by gas chromatogra-
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