合成カンナビノイドJWH-018、JWH-073、JWH-122及びそれらの異性体の識別

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1 59 * *, ** * * * * Identification of cannabimimetic indoles ; JWH-018, JWH-073, JWH-122 and their structural isomers Seiko KATAGI*, Taichi NAIKI*, **, Masato OGINO*, Junichi ISHIKAWA*, Kazuyoshi KOSONE* and Mitsuhiro YAMAZAKI * *Tokyo Customs Laboratory , Aomi, Koto-ku, Tokyo Japan ** Present address : Post Clearance Audit, Investigation and Intelligence Division , Aomi, Koto-ku, Tokyo Japan JWH-018, JWH-073 and JWH-122, which are controlled substances, have structural isomers. Not all of these structural isomers are controlled, because control laws do not cover all of these structural isomers. Therefore, precise identification of the structural isomers is required for accurate analysis. The purpose of this study was to identify JWH-018, JWH-073, JWH-122 and their structural isomers by IR, GC-MS and 1H NMR. As a result, it was found that IR spectra differed for each isomer, and all samples in this study could be identified by GC-MS and 1H NMR. Furthermore, the use of multiple instruments enabled more accurate analysis. JWH 1), 2) 21 1-(1--1H- -3-)JWH (1--1H--3-)(-1-) JWH ( H--3-)(-1-) JWH-015(4--1-)(1- -1H--3-)JWH JWH-018 JWH JWH-015 JWH JWH-018JWH-073 JWH-122 IR GC-MS 1 H NMR 2.1 Table 1 3) A 2 B 4 C C 341 JWH-A * **

2 60 Table 1 Structural formula and molecular weights of samples JWH-073Cayman JWH-018 (1--1H--3-)(-1-) JWH-019Cayman JWH-015SIGMA-ALDRICH JWH ACROS ORGANICS SIGMA-ALDRICH 1-SIGMA-ALDRICH 1.0 M solution in hexanes SIGMA-ALDRICH Q-23, μm mesh n- n- n- n (1) EI Agilent 7890GC/5975MS DB-5MS 30 m0.25 mm I.D., 0.25 μmagilent 801 min40/min32010 min m/z 2.2.1(2) CI HP 6890GC/5975MS DB-5MS 30 m0.25 mm I.D., 0.25 μmagilent 801 min40/min32010 min m/z Varian Mercury H -d2, 99.9 %NMR Nicolet ( H--3-)(-1-) JWH-016

3 61 O OH O Cl N CH 3 N R CH 3 Fig. 1 Reaction route of synthesis of JWH-016 O N CH 3 ( H--3-)(-1- )JWH-007 (4--1-)(1--1H--3- )JWH-120 (4--1-)(1--1H--3-) JWH-A 1), 4)6) Friedel-Crafts JWH-016 Fig (1) JWH-016 JWH JWH-120 JWH-A 1.7 mmol 7.0 ml 1.0 ml JWH-016 JWH JWH-120 JWH-A GC-MS 2.3.2(2) 2-JWH-016 JWH-007 JWH-120 JWH-A 1.3 mmol 0.50 g 5.0 ml 1-JWH JWH-016 JWH-A 1- JWH ml 80 /=1/ H-JWH H-JWH H-JWH H-JWH-A GC-MS 2.3.2(3) 2.3.2(2) 7.0 ml 1 M 2.42 ml (1) 7.0 ml 3 10 ml 55 / =1/1 GC-MS 1 H NMR 2.4 IR KBr IR 2.5 GC-MS EI-MS EI-MS Retention Index EI 3135 Ia 7) Ia = 100 n ( ( t Ra t Rn ) / (t Rn+1 t Rn ) ) n t Ra [min] t Rn [min]

4 62 t Rn+1 [min] H NMR -d2 1 H NMR 3.1 CI-MS EI-MS 1 H NMR 1), 5) 1), 5) JWH H NMR Fig IR IR IR 3.3 GC-MS EI-MS EI-MS Fig.9 AFig.10 B Fig.11 C EI-MS Fig.12Fig.13 Fig.14 Table 2 JWH-073 Fig.15 11) O N O Fig. 2 1 H NMR spectra of JWH IR IR IR Fig.3 AFig.4 B Fig.5 C IR cm cm cm cm -1 C-H 8) 1480 cm -1 9) 1650 cm -1 C=O 10) IR IR JWH-073JWH-015 JWH-120 IR Fig.6 JWH-018JWH-016 JWH-A IR Fig.7 JWH-019JWH-007 JWH-122 IR Fig.8 IR N Fig. 15 Proposed EI-fragmentation of JWH-073 based on accurate masses and elemental compositions of the fragment ions EI-MS Fig.9Fig.10 Fig.11 m/z RCO + RCO + Fig.9Fig.10 Fig.11 RCO +

5 Table 2 B A C H NMR 327 JWH-073A JWH-015 B JWH-120C 1 H NMR Fig.16 JWH-015 JWH H NMR Fig ppm JWH-073 JWH-015 JWH B C Fig ppm A JWH-073JWH-018 JWH H NMR Fig.17 1 H NMR Fig ppm JWH-073 JWH-018 JWH B C 8.0 ppm Fig.17 B C 9 1 H NMR JWH-018JWH-073JWH IR EI-MS 1 H NMR EI-MS 1 H NMR JWH-018JWH-073JWH-122 IR 1) John W. Huffman, Gulay Zengin, Ming-Jung Wu, Jianzhong Lu, George Hynd, Kristen Bushell, Alicia L. S. Thompson, Simon Bushell, Cindy Tartal, Dow P. Hurst, Patricia H. Reggio, Dana E. Selley, Michael P. Cassidy, Jenny L. Wiley and Billy R. MartinBioorganic & Medicinal Chemistry, 13, 89 (2005). 2) Manera Clementina, Tuccinardi Tiziano, Martinelli AdrianoMini-Reviews in Medical Chemistry, 8, 370 (2008). 3) David NuttACMD report on the major cannabinoid agonists, P.1 (2009). 4) John W. Huffman, Dong Dai, Billy R. Martin and David R. ComptonBioorganic & Medicinal Chemistry Letters, 4, 563 (1994). 5) John W. Huffman, Ross Mabon, Ming-Jung Wu, Jianzhong Lu, Richard Hart, Dow P. Hurst, Patricia H. Reggio, Jenny L. Wiley and Billy R. MartinBioorganic & Medicinal Chemistry, 11, 539 (2003). 6) John W. Huffman, Paul V. Szklennik, Amanda Almond, Kristen Bushell, Dana E. Selley, Hengjun He, Michael P. Cassidy, Jenny L. Wiley and Billy R. MartinBioorganic & Medicinal Chemistry Letters, 15, 4110 (2005). 7) P.309 (1998). 8) R. M. SilversteinMS, IR, NMR 6 P.90 (2000). 9) 5 P.65 (1994). 10) R. M. SilversteinMS, IR, NMR 6 P.97 (2000). 11) Rainer Lindigkeit, Anja Boehme, Ina Eiserloh, Maike Luebbecke, Marion Wiggermann, Ludger Ernst and Till BeuerleForensic Science International, 191, 58 (2009).

6 64 Fig. 3 IR spectra of JWH-073, JWH-018 and JWH-019 (Series A) Fig. 4 IR spectra of JWH-015, JWH-016 and JWH-007 (Series B)

7 65 Fig. 5 IR spectra of JWH-120, JWH-A and JWH-122 (Series C) Fig. 6 IR spectra of JWH-073 (Series A), JWH-015 (Series B) and JWH-120 (Series C)

8 66 Fig. 7 IR spectra of JWH-018 (Series A), JWH-016 (Series B) and JWH-A (Series C) Fig. 8 IR spectra of JWH-019 (Series A), JWH-007 (Series B) and JWH-122 (Series C)

9 67 Fig. 9 EI-MS spectra of JWH-073, JWH-018 and JWH-019 (Series A) Fig. 10 EI-MS spectra of JWH-015, JWH-016 and JWH-007 (Series B) Fig. 11 EI-MS spectra of JWH-120, JWH-A and JWH-122 (Series C)

10 68 Fig. 12 EI-MS spectra of JWH-073 (Series A), JWH-015 (Series B) and JWH-120 (Series C) Fig. 13 EI-MS spectra of JWH-018 (Series A), JWH-016 (Series B) and JWH-A (Series C) Fig. 14 EI-MS spectra of JWH-019 (Series A), JWH-007 (Series B) and JWH-122 (Series C)

11 69 Table 2 EI-MS data of samples Fig H NMR spectra of JWH-073 (Series A), JWH-015 (Series B) and JWH-120 (Series C) ( 1 H signals from the alkyl groups, 1 H signals from the aromatic groups, 1 H signals from the methyl groups bonding to the aromatic rings) Fig H NMR spectra of JWH-073, JWH-018 and JWH-019 (Series A) ( 1 H signals from the alkyl groups, 1 H signals from the aromatic groups)

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-d

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-d 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,