Analytical and Bioanalytical Chemistry

, Volume 405, Issue 9, pp 2931–2941 | Cite as

Influence of precursor solvent extraction on stable isotope signatures of methylamphetamine prepared from over-the-counter medicines using the Moscow and Hypophosphorous routes

  • Niamh NicDaéid
  • Saravana Jayamana
  • William J. Kerr
  • Wolfram Meier-Augenstein
  • Helen F. Kemp
Original Paper

Abstract

A number of methods of clandestine manufacture of methylamphetamine involve the extraction and subsequent reaction of pseudoephedrine hydrochloride with other essential chemicals. The precursor can be easily extracted from over-the-counter medication widely available in the UK and elsewhere. Essential chemicals such as iodine and red phosphorous are also readily available and can be extracted from iodine tinctures and matchboxes, respectively. This work reports the repetitive preparation of methylamphetamine using two popular routes (the Moscow and Hypophosphorous synthesis). The focus was on the extraction solvent used for isolation of the precursor chemical and any consequential isotopic variation which may arise in the final product. Six batches of methylamphetamine were prepared under precisely controlled conditions for each synthetic route and for each of three different precursor extraction solvents. Synthesis of the final product from laboratory grade precursor using the synthetic methods described was used as a template for comparison. The resultant IRMS data from all 48 prepared samples suggests some underlying trends in the identification of the synthetic route which may aid in the interpretation of IRMS data derived from clandestine samples.

Keywords

Precursor Solvent extraction IRMS Methylamphetamine 

References

  1. 1.
    United Nations Office on Drugs and Crime (2011) World drug report, UNODC.Google Scholar
  2. 2.
    Uncle F (2009) Secrets of methamphetamine manufacture. Vol.9th edition. Loompanics Unlimited, Port Townsend, WashingtonGoogle Scholar
  3. 3.
    Kunalan V, Kerr WJ, NicDaeid N (2012) Investigation of the reaction impurities associated with methylamphetamine synthesized using the Nagai method. Anal Chem 84:5744–5752CrossRefGoogle Scholar
  4. 4.
    Skinner HF (1990) Methamphetamine synthesis via HI/red phosphorous reduction of ephedrine. For Sci Int 48:128–134Google Scholar
  5. 5.
    Albouy D, EtemadMoghadam G, Vinatoru M, Koenig M (1997) Regenerative role of the red phosphorus in the couple ‘HIaq/Pred’. J Organomet Chem 529:295–299CrossRefGoogle Scholar
  6. 6.
    Kurashima N, Makino Y, Urano Y, Sanuki K, Ikehara Y, Nagano T (2009) Use of stable isotope ratios for profiling of industrial ephedrine samples: application of hydrogen isotope ratios in combination with carbon and nitrogen. For Sci Int 189(1–3):14–18Google Scholar
  7. 7.
    Collins M, Cawley AT, Heagney AC, Kissane L, Robertson J, Salouros H (2009) δ13C, δ15N and δ2H isotope ratio mass spectrometry of ephedrine and pseudoephedrine:application to methylamphetamine profiling. Rapid Comm Mass Spec 23(213):003–2010Google Scholar
  8. 8.
    David GE, Coxon A, Frew RD, Hayman AR (2010) Isotope fractionation during precipitation of methamphetamine HCl and discrimination of seized forensic samples. For Sci Int 200(1–3):123–129Google Scholar
  9. 9.
    Buchanan HAS, NicDaeidN, Meier-Augenstein W, Kemp HF, Kerr WJ, Middleditch M (2008) Emerging use of isotope ratio mass spectrometry as a tool for discrimination of 3,4-methylenedioxymethamphetamine by synthetic route. Anal Chem 80(9):3350–3356CrossRefGoogle Scholar
  10. 10.
    De Korompay A, Hill JC, Carter JF, Nic Daeid N, Sleeman R (2008) Supported liquid-liquid extraction of the active ingredient (3,4-methylenedioxymethylamphetamine) from ecstasy tablets for isotopic analysis. J Chromatogr A 1178:1–8CrossRefGoogle Scholar
  11. 11.
    NicDaeid N, Meier-Augenstein W (2008) Feasibility of source identification of seized street drug samples by exploiting differences in isotopic composition at natural abundance level by GC/MS as compared to isotope ratio mass spectrometry (IRMS). For Sci Int 174(2–3):259–260Google Scholar
  12. 12.
    Carter JF, Titterton EL, Murray M, Sleeman R (2002) Isotopic characterisation of 3,4-methylenedioxyamphetamine and 3,4-methylenedioxymethylamphetamine (ecstasy). Analyst 127(6):830–833CrossRefGoogle Scholar
  13. 13.
    Carter JF, Titterton EL, Grant H, Sleeman R (2002) Isotopic changes during the synthesis of amphetamines. Chem Comm 21:2590–2591CrossRefGoogle Scholar
  14. 14.
    Iwata YT, Kuwayama K, Tsujikawa K, Miyaguchi H, Kanamori T, Inoue H (2008) Evaluation method of linking methamphetamine seizures using stable carbon and nitrogen isotopic compositions: a complementary study with impurity profiling. Rapid Comm Mass Spec 22(23):3816–3822CrossRefGoogle Scholar
  15. 15.
    Kurashima N, Makino Y, Sekita S, Urano Y, Nagano T (2004) Determination of origin of ephedrine used as precursor for illicit methamphetamine by carbon and nitrogen stable isotope ratio analysis. Anal Chem 76(14):4233–236CrossRefGoogle Scholar
  16. 16.
    Makino Y, Urano Y, Nagano T (2005) Investigation of the origin of ephedrine and methamphetamine by stable isotope ratio mass spectrometry: a Japanese experience. Bull Narc 57:63–68Google Scholar
  17. 17.
    NicDaéid N, Meier-Augenstein W, Helen F, Kemp HF, Sutcliffe OB (2012) Using isotopic fractionation to link precursor to product in the synthesis of (±)-mephedrone. A new tool for combating ‘legal high’ drugs. Anal Chem 84(20):8691–8696CrossRefGoogle Scholar
  18. 18.
    Matthew M, Palenik GJ (1997) The crystal and molecular structures of (+)-pseudoephedrine and (+)-pseudoephedrine hydrochloride. Acta Crystallogr Crystal Chem B33:1016–1022Google Scholar
  19. 19.
    Kram TC, Kruegel AV (1977) The identification of impurities in illicit methamphetamine exhibits by gas chromatography/mass spectrometry and nuclear magnetic resonance spectroscopy. J For Sci 22(1):40–52Google Scholar
  20. 20.
    Landwehr JM, Meier-Augenstein W, Kemp HF (2011) A counter-intuitive approach to calculating non-exchangeable H-2 isotopic composition of hair: treating the molar exchange fraction f(E) as a process-related rather than compound-specific variable. Rapid Commun Mass Spec 25:301–306CrossRefGoogle Scholar
  21. 21.
    Paul D, Skrzypek G, Forizs I (2007) Normalization of measured stable isotope composition to isotope reference scale—a review. Rapid Comm Mass Spec 21:3006–3014CrossRefGoogle Scholar
  22. 22.
    Meier-Augenstein W (2010) Stable isotope forensics: an introduction to forensic application of stable isotope analysis. Wiley, Chichester, UKGoogle Scholar
  23. 23.
    Coplen TB (2011) Guidelines and recommended terms for expression of stable-isotope-ratio and gas-ratio measurement results. Rapid Comm Mass Spec 25:2538–2560Google Scholar
  24. 24.
    Andrews KM (1995) Ephedra’s role as a precursor in the clandestine manufacture of methamphetamine. J For Sci 40(4):551–560Google Scholar
  25. 25.
    Meier-Augenstein W, Chartrand MMG, Kemp HF, St-Jean G (2011) An inter-laboratory comparative study into sample preparation for both reproducible and repeatable forensic (2)H isotope analysis of human hair by continuous flow isotope ratio mass spectrometry. Rapid Comm Mass Spec 25:3331–3338CrossRefGoogle Scholar
  26. 26.
    Coplen TB, Qi HP (2012) USGS42 and USGS43: human-hair stable hydrogen and oxygen isotopic reference materials and analytical methods for forensic science and implications for published measurement results. For Sci Int 214:135–141Google Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2012

Authors and Affiliations

  • Niamh NicDaéid
    • 1
  • Saravana Jayamana
    • 1
  • William J. Kerr
    • 2
  • Wolfram Meier-Augenstein
    • 3
    • 4
  • Helen F. Kemp
    • 3
  1. 1.Department of Pure and Applied Chemistry, Centre for Forensic ScienceUniversity of StrathclydeGlasgowUK
  2. 2.Department of Pure and Applied Chemistry, WestCHEMUniversity of StrathclydeGlasgowUK
  3. 3.Stable Isotope Forensics LaboratoryJames Hutton InstituteInvergowrie, DundeeUK
  4. 4.Environmental and Forensic Science GroupRobert Gordon UniversityAberdeenUK

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