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A STATISTICAL EVALUATION OF THE CHEMICAL COMPOSITION OF HEROIN SAMPLES WITH THE VIEW TO DISCRIMINATING BETWEEN THEIR POSSIBLE SOURCES A. EKANGAKI, PHD J. SKOPEC, PHD, Z.
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Forensic Science International 164 (2006) 221–229
www.elsevier.com/locate/forsciint
Chemistry Building, School of Environmental and Life Sciences, The University of Newcastle, University Drive, Callaghan, NSW 2308, Australia
b
Abstract
Treatment of morphine, at room temperature, with a mixture of trifluoroacetic anhydride (TFAA) and acetic acid (20–30 min) affords good yields of heroin. GC–
MS and HPLC examination shows that heroin produced by this route to be extremely clean, but the product contains slightly less heroin than observed via the more
traditional acetic anhydride (AA) route (76.1% versus 83.55%); and greater quantities of 3-MAM and 6MAM (6.9% versus 0.75% and 7.13% versus 0.63%). The
concentration ratios of the major alkaloid impurities were found to be both production method (TFAA and AA) as well as morphine extraction methodology
dependant. Data contained herein describe the impact of this new production method on current intelligence efforts, largely by-passing existing heroin signature
programs and the UNDCP’s efforts to restrict access to key synthetic precursors. Given the methodology dependency we find that examination of the major alkaloid
ratios is unsuitable for the development of a new heroin signature program.
Further examination of the TFAA methodology allowed the identification of TFAA specific marker compounds, namely bis-trifluoroacetylmorphine (30), 3-
trifluoroacetyl-6-acetylmorphine (31), 3-acetyl-6-trifluoroacetylmorphine (32) and trifluoroacetylcodeine (33). However, the hydrolytic lability of trifluroacetyl esters
requires careful treatment of suspect samples, thus we propose a modification to existing HSP’s in instances were the 6-MAM/WM ratio falls within the average
minimum and maximum values of 6.17 and 17.32. # 2006 Elsevier Ireland Ltd. All rights reserved.
Keywords: Heroin; Signaure program; Acetylation of morphine; Cold synthesis
identifying new
production processes
[31].
To date HSP analysis
rapidly allows South-
West Asian
(SWA) heroin to be
identified by
significant quantities
of both
0379-0738/$ – see front matter # 2006 Elsevier Ireland Ltd. All rights reserved. doi:10.1016/j.forsciint.2006.02.009
alkaloids; Mexican
Fig. 1. Acetylation of morphine to yield diacetylmorphine (DAM, heroin).
heroin by its unique
appearance; and South
American heroin by its
high purity and low
Fig. 2. Route specific markers detected in the illicit production of heroin.
acetyl codeine (AC)
papaverine (PAP) and
content. Further,
noscapine (NOS);
quantitative major
South-East Asian
component data have
(SEA) heroin by an
been used successfully
absence of these
L.R. Odell et al./Forensic Science International 164 (2006) 221–229 225
Fig. 3. Chemical structures of the major alkaloids found in, and as a result of, the illicit synthesis of heroin.
L.R. Odell et al./Forensic Science International 164 (2006) 221–229 229
Table 1
Comparison of chemical yields and major component analyses for the synthesis of heroin via the TFAA or the AA route
Method Target compounds
gas chromatograph
AA; requires heating 80–90 8C.
the potential to
1.48 0.22 0.01 0.02 0.80 0.36
TFAAd 1.14 0.10 <0.01 0.01 0.02 9.86 1.86
SWA
circumvents the
AAe 10.69 0.46 33.1 1.25 4.61 0.13 1.11 0.39
TFAAf 10.92 1.58 24.45 8.63 4.7 1.04 12.35
4.27
current UNDCP
SEAAAe
8.94 0.3 0.21 0.18 0.21 0.23 0.28 0.03
TFAA Basee 9.07 0.09 0.25 0.22 0.06 0.2 9.54 2.7
methods of tracking
TFAA HClg 9.78 0.07 2.12 0.34 0.26 0.1 9.03 1.31
Average
AAh 5.56 4.35 6.68 13.93 0.99 1.91 0.71 0.42
TFAAi
a
heroin production [43].
6.5 4.59 6.58 11.34 1.24 2.11
2.79
10.27
From Table 1, it is
Tas: Tasmanian procedure; SWA: South-West Asian procedure; SEA:
South-East Asian procedure.
b
C = total codeine (C + AC); WM = (%DAM 285.34/
enforcement
perspective the outwith that
discovery of such a anticipated in current
simple, rapid and HSP’s. As can be seen
facile method for from Table 1 the
DAM synthesis is product produced via
234 L.R. Odell et al./Forensic Science International 164 (2006) 221–229
Fig. 4. Trace level impurities targeted by the Australian National Heroin Signature Program.
L.R. Odell et al./Forensic Science International 164 (2006) 221–229 237
extraction and
consequently had the
238 L.R. Odell et al./Forensic Science International 164 (2006) 221–229
significant differences
in the quantities of morphine and codeine
morphine related N-oxide, which are
byproducts; 11–13 and transient intermediates
15 are produced when formed during the
AA is employed as the acetylation process
acetylating agent, e.g. [22]. Not surprisingly
13: 38.74, 51.13 and our data confirm the
100 for the Tas, SWA TFAA routes as milder,
and SEA Base resulting in lower
methods, respectively, initial concentrations
as compared with the of these intermediate
TFAA method, e.g. 13: species and hence
7.19, 9.92 and 50.33 lower amounts of 11–
for the Tas, SWA and 13 and 15.
SEA methods,
respectively. These
compounds are formed
L.R. Odell et al./Forensic Science International 164 (2006) 221–229 241
AAd TFAAd
AAb TFAAc AAd TFAAd
Morphine related compounds 0.37
11 0.39 0.04 0.07 0.04 17.48 1.97 2.47 0.05 0.58 0.14 0.12
12 14.91 0.98 4.46 1.5 20.58 2.01 10.95 2.54 35.96 6.46 20.25
6.33
13 38.74 1.22 7.19 3.25 51.13 0.85 9.92 2.0 100 5.30 50.33
18.1
14 <0.05 <0.05 2.8 0.54 0.83 0.67 0.04 0.02 0.09
0.04
15 2.56 0.37 0.3 0.16 12.85 1.16 1.82 0.11 18.17 4.70 6.52
2.13
16 <0.05 <0.05 4.19 0.02 0.13 0.1 0.16 0.05 0.17
0.07
Thebaine related compounds 0.4
17 2.13 0.13 0.16 0.06 61.36 4.14 1.76 0.69 0.2 0.06 0.05
18 5.32 0.01 2.1 1.28 100 18.32 20.75 2.45 2.41 0.08 1.45
0.33
19 6.16 0.55 0.47 0.34 97.79 10.56 4.75 0.35 0.84 0.09 0.02
0.01
20 0.22 0.03 0.09 0.03 4.87 0.13 0.34 0.26 0.24 0.07 0.2
0.09
21 0.12 0.02 <0.05 9.11 1.69 0.92 0.31 0.03 0.08 0.02
0.02
22 <0.05 <0.05 3.11 1.25 0.73 0.52 0.01 0.01 <0.05
23 <0.05 <0.05 6.22 0.85 <0.05 <0.05 <0.05
Noscapine and N-norlaudanosine related compounds
24 <0.05 <0.05 0.26 0.05 <0.05 <0.05 <0.05
25 <0.05 <0.05 0.18 0.01 <0.05 <0.05 <0.05
26 <0.05 <0.05 57.21 1.33 3.52 0.02 1.5 0.23 <0.05
27 <0.05 <0.05 1.57 0.01 0.14 0.03 <0.01 <0.05
28 <0.05 <0.05 2.28 0.10 0.06 0.05 <0.01 <0.05
29 0.22 0.15 <0.05 8.73 3.8 5.93 0.38 100 9.9 7.74
0.25
a
Response was calculated against an internal standard (i.e. compound response/internal standard 100), data are then normalised against largest response.
n = 3.
n = 6.
n = 2.
242 L.R. Odell et al./Forensic Science International 164 (2006) 221–229
determined to have
[M]+ of 395, which is
consistent with the
addition of a
trifluoroacetyl group to
codeine. This was
confirmed by the [M-
CF3COOH]+ (m/ z =
282) base ion. The
spectrum of 31 also
showed characteristic
codeine skeleton
fragmentation peaks at
m/z 229 and 188
supporting the
assignment of 31 as
trifluoroacetylcodeine
[45,46].
250 L.R. Odell et al./Forensic Science International 164 (2006) 221–229
Fig. 6. (a) Chemical structures of TFAA specific markers identified in this work; (b) GC/MS trace of the crude reaction mixture arising from the reaction of morphine and AA; (c) GC/MS
trace of the crude reaction mixturearising from the reaction of morphineand TFAA; (d) GC/MS trace of the crude reaction of codeine and AA; (e) GC/MS trace of the crude mixture arising
from the reaction of codeine and TFAA. (f) GC–MS trace typical of DAM synthesis using TFAA; expanded section shows the presence of 3-acetyl-6-trifluoroacetylmorphine (32) and
trifluoroacetylcodeine (33).
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