3 * * * * * Analytical data of designer drugs of synthetic phenethylamines Ryosuke SASAKI*, Miho KAT*, Tsuyoshi MATSUMT*, Akira UDAGAWA* and Ryuichi MATSUZAKI* *Tokyo Customs Laboratory 2-7-11, Aomi, Koto-ku, Tokyo 135-15 Japan In recent years, so-called designer drugs, which are chemicals whose structures are similar to illicit drugs, have been widely distributed and abused in Japan. Synthetic phenethylamines, one group of designer drugs, have similar structures to stimulants, and also stimulate the central nervous system like stimulants. In this study, we classified synthetically produced phenethylamine samples according to their chemical structures, and analyzed them using an infrared spectrometer (IR), gas chromatograph mass spectrometer (GC-MS), liquid chromatograph mass spectrometer coupled with photodiode array detector (LC-PDA-MS) and nuclear magnetic resonance (NMR) spectrometer. 2 2 12 27 3 7 IR GC-MS LC-PDA-MS NMR 2.1 2.1.1 12 25 1 27 2 Table 1 Fig.1 2.1.2 TFA TFAA * 135-15 2-7-11
Group A (2,5-Dimethoxyphenyl type) 25D-NBMe (1) 25B-NBMe (2) 25I-NBMe (3) 25C-NBF () 25B-NBF (5) Group B (Benzofuran-2-yl type) Group C (-Alkoxy-3,5-dimethoxyphenyl type) 2-MAPB () 3C-E () 2-EAPB (7) Allylescaline (9) Group D (thers) 3-FPM (10) 5-APDB (11) Prolintane (12) Fig.1 Chemical structures of synthetic phenethylamines used in this study
5 Table 1 Synthetic phenethylamines used in this study Sample Number Chemical Name Common Name Mw 1 N-(2-Methoxybenzyl)- 2-(2,5-dimethoxy--methylphenyl)ethanamine 25D-NBMe 315 2 2-(-Bromo-2,5-dimethoxyphenyl)-N-(2-methoxybenzyl)ethanamine 25B-NBMe 30 3 2-(-Iodo-2,5-dimethoxyphenyl)-N-(2-methoxybenzyl)ethanamine 25I-NBMe 27 2-(-Chloro-2,5-dimethoxyphenyl)-N-(2-fluorobenzyl)ethanamine 25C-NBF 323 5 2-(-Bromo-2,5-dimethoxyphenyl)-N-(2-fluorobenzyl)ethanamine 25B-NBF 3 1-(Benzofuran-2-yl)-N-methylpropan-2-amine 2-MAPB 19 7 1-(Benzofuran-2-yl)-N-ethylpropan-2-amine 2-EAPB 203 1-(-Ethoxy-3,5-dimethoxyphenyl)propan-2-amine 3C-E 239 9 2-(-Allyloxy-3,5-dimethoxyphenyl)ethanamine Allylescaline 237 10 2-(3-Fluorophenyl)-3-methylmorpholine 3-FPM 195 11 1-(2,3-Dihydrobenzofuran-5-yl)propan-2-amine 5-APDB 17 12 1-(1-Phenylpentan-2-yl)pyrrolidine Prolintane 217 2.2 2.2.1 IR Nicolet700 000-00 cm -1 2 cm -1 32 KBr 2.2.2 GC-MS Agilent 790(GC)/5975(MS) DB-5MS 30 m 0.25 mm I.D.,0.25 μm (Agilent) 0 C(1 min) (0 C/min) 320 C(5 min) 320 C 1 μl 50 : 1 320 C EI 70 V 230 C 33-550 37.0 cm/s 2.2.3 LC-PDA-MS Agilent 120 infinity XBridge C1 150 mm 2.1 mm I.D., 3.5 μm (Waters) 0 C A:10 mm B: A/B = 30/70 0.30 ml/min 1 μl (PDA) PDA 10-00 nm (Agilent120) 3500 V 70 V ESI 2.2. NMR Varian Mercury-300 (300 MHz) 1 H 1 2.3 2.3.1 IR KBr IR 2.3.2 GC-MS 2.3.2.1 EI 1 mg 1 mol/l 0.5 ml 1 ml EI 2.3.2.2 TFA 1-11 1 mg TFAA 0.2 ml 70 C 30 TFAA 1 ml EI
2.3.3 LC-PDA-MS 1 mg 10 ml 2.3. NMR 10-30 mg 0.7 ml 1. ml 1 H-NMR 3.1 IR 200-2500 cm -1 100-1575 cm -1 N 1) IR Fig.2-1 2-2 2-3 2-3.2 GC-MS 3.2.1 EI 3.2.1.1 Group A 2,5- Fig.1 1 2 3 5 EI Fig.3-1 1 2 3 150 1 1 2 230 232 3 27 5 109 13 1 5 230 232 3.2.1.2 Group B -2- Fig.1 7 EI Fig.3-2 7 131 5 7 72 3.2.1.3 Group C - -3,5- Fig.1 9 EI Fig.3-3 9 17 19 9 237 3.2.1. Group D Fig.1 10 11 12 EI Fig.3-3.2.2 TFA -EI 3.2.2.1 Group A 2,5- Fig.1 1 2 3 TFA EI Fig.-1-1 5 TFA EI Fig.-1-2 1 2 3 1 15 17 2 229 231 22 2 3 277 290 5 109 15 19 5 229 231 22 2 3.2.2.2 Group B -2- Fig.1 7 TFA EI Fig.-2 7 131 15 110 15 7 1 3.2.2.3 Group C - -3,5- Fig.1 9 TFA EI Fig.-3 9 17 10 195 223 9 12 151 179 207 293 3.2.2. Group D Fig.1 10 11 TFA EI Fig.- 3.3 LC-PDA-MS 3.3.1 ESI ESI Fig.5 [M+H] + 25C-NBF () 32 32 3 1 25B-NBMe (2) 30 32 1 1 25B-NBF (5) 3 370 1 1 Cl 35 Cl 75.77% 37 Cl 2.23% 3 1Br 79 Br 50.9% 1 Br 9.31% 1 1 Cl 1 2 5 Br 1 3.3.2 UV UV 220-00 nm 2) UV Fig. 3.3.2.1 Group A 2,5- Fig.1 1 21 nm 2-5 300 nm 1 2-5 2,5-1 2-5 3.3.2.2 Group B -2- Fig.1 7 2 nm 27 nm
7 2 3.3.2.3 Group C - -3,5- Fig.1 9 270 nm 3 5 3. NMR 1 2 3 1 H-NMR Fig.7-1-1 5 1 H-NMR Fig.7-1-2 7 1 H-NMR Fig.7-2 9 1 H-NMR Fig.7-3 10 11 12 1 H-NMR Fig.7- IR GC-MS LC-PDA-MS NMR IR EI ESI UV 1 H-NMR 1) R. M. Silverstein, F. X. Webster and D. J. Kiemle -MS, IR, NMR - 7, P. 10 (200), ( ) 2) M. Hesse, H. Meier and B. Zeeh-UV, IR, NMR, MS - 2, P. 2 (2010), ( )
25D-NBMe (1) 25B-NBMe (2) 25I-NBMe (3) Fig.2-1 IR spectra of 1-3 hydrochloride
9 25C-NBF () 25B-NBF (5) 2-MAPB () Fig.2-2 IR spectra of - hydrochloride
50 2-EAPB (7) 3C-E () Allylescaline (9) Fig.2-3 IR spectra of 7-9 hydrochloride
51 3-FPM (10) 5-APDB (11) Prolintane (12) Fig.2- IR spectra of 10-12 hydrochloride
52 150 230, 1 232 +H +H 150 150 Br 150 H N 1 25D-NBMe (1) 230, 25B-NBMe (2) 232 150 27 +H 109 13 1 +H H N 109 150 25I-NBMe (3) 1 Cl 13 25C-NBF () F 27 109 13 230, 232 +H H N 109 Br 13 F 230, 232 25B-NBF (5) 100 200 300 Fig.3-1 EI-MS spectra of Group A
53 5 5 72 72 131 131 131 2-MAPB () 131 2-EAPB (7) Fig.3-2 EI-MS spectra of Group B 19 17 17 19 +H +H 17 237 17 3C-E () Allylescaline (9) Fig.3-3 EI-MS spectra of Group C 71 95 123 71 13 +H 13 95 123 195 3-FPM (10) 5-APDB (11) 12 12 N 17 Prolintane (12) 17 Fig.3- EI-MS spectra of Group D
5 17 15 17 15 11 25D-NBMe (1) 22 2 229, 231 22, 2 229, 231 75 77 25B-NBMe (2) 290 277 290 25I-NBMe (3) 277 523 Fig.-1-1 EI-MS spectra of TFA derivatives of Group A
55 109 19 15 19 109 15 19 25C-NBF () 109 22 2 229, 231 22, 2 109 229, 231 3 5 25B-NBF (5) Fig.-1-2 EI-MS spectra of TFA derivatives of Group A
5 15 15 15 131 N 110 131 15 CF 3 110 25 2-MAPB () 15 1 1 131 N 10 15 CF 3 10 131 2-EAPB (7) 299 Fig.-2 EI-MS spectra of TFA derivatives of Group B 17 10 195 223 10 195 223 335 +H 17 3C-E () 17 12 151 179 207 293 333 +H 293 12 207 +H 17 179 151 Allylescaline (9) Fig.-3 EI-MS spectra of TFA derivatives of Group C
57 70 17 +H 70 95 123 +H 9 17 95 9 123 3-FPM (10) 290 133 10 133 5-APDB (11) 10 273 Fig.- EI-MS spectra of TFA derivatives of Group D
5 Group A 25D-NBMe (1) 25B-NBMe (2) 25I-NBMe (3) 31 30 [M+H] + [M+H] + 32 2 [M+H] + 25C-NBF () 25B-NBF (5) 32 3 370 [M+H] + [M+H] + 32 Group B 2-MAPB () 2-EAPB (7) 190 20 [M+H] + [M+H] + Group C 3C-E () Allylescaline (9) 20 23 [M+H] + [M+H] + Group D 3-FPM (10) 5-APDB (11) 19 17 [M+H] + [M+H] + 11 Prolintane (12) 21 [M+H] + Fig.5 ESI-MS spectra
59 Group A 25D-NBMe (1) 25B-NBMe (2) 25I-NBMe (3) 21 29 302 nm nm nm 25C-NBF () 25B-NBF (5) Group B 2 2 27 2-MAPB () 2-EAPB (7) 27 Group C 3C-E () Allylescaline (9) 270 270 nm nm Group D 3-FPM (10) 5-APDB (11) Prolintane (12) 22 25 259 nm nm nm Fig. UV spectra
0 25D-NBMe (1) 3, Me1-3 1, 2 3, 5, 3, Me 25B-NBMe (2) 3, Me1-3 1, 2 CHCl 3 3 3, 5, 25I-NBMe (3) 3, Me1-3 1, 2 3, 3, 5 Fig.7-1-1 1 H-NMR spectra of Group A
1 25C-NBF () 3, Me1, Me2 CHCl 3 3, 5 3, 1, 2 H 2 25B-NBF (5) 3, Me1, Me2 CHCl 3 3, 5 3, 1, 2 H 2 Fig.7-1-2 1 H-NMR spectra of Group A
2 2-MAPB () 1 CHCl 3 3, 7 5, 2 3 1 H 2 3, 2 2-EAPB (7) 5,, 7 CHCl 3 3 2 1, 1 H 2 Fig.7-2 1 H-NMR spectra of Group B 3C-E () Me1, Me2 CHCl 3 2, 1 2 1 2 3 Allylescaline (9) Me1, Me2 2, CHCl 3 2 3 1 2 1 Fig.7-3 1 H-NMR spectra of Group C
3 3-FPM (10) 3 5 2,, 1 2 1 2 5-APDB (11) 3 2 CHCl 3 7 3 2 1 Prolintane (12) 2, 3, 5 3-5 2, 2, 5 1 3, Fig.7-1 H-NMR spectra of Group D