Halogenated solvent interactions with N,N-dimethyltryptamine: formation of quaternary ammonium salts and their artificially induced rearrangements during analysis.
Simon D Brandt, Cláudia P B Martins, Sally Freeman, Nicola Dempster, Philip G Riby, Jochen Gartz, John F Alder
Forensic science international July 4, 2008 Peer reviewed DOI: 10.1016/j.forsciint.2008.03.013 via PubMed
Summary
DMT reacts with dichloromethane to produce a quaternary N-chloromethyl ammonium salt, which undergoes rearrangement during gas chromatography-mass spectrometry analysis, yielding various products. The study also explores DMT's interactions with other halogenated solvents like dibromomethane and 1,2-dichloroethane, resulting in multiple rearrangement products. Insights into the rearrangement mechanisms were gained using deuterated compounds, potentially aiding in identifying solvents used in the production of controlled substances.
Study at a glance
| Key finding | DMT forms a quaternary N-chloromethyl ammonium salt upon reaction with dichloromethane, which rearranges during analysis, producing several by-products. |
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Abstract
The psychoactive properties of N,N-dimethyltryptamine (DMT) 1a are known to induce altered states of consciousness in humans. This particular attribute attracts great interest from a variety of scientific and also clandestine communities. Our recent research has confirmed that DMT reacts with dichloromethane (DCM), either as a result of work-up or storage to give a quaternary N-chloromethyl ammonium salt 2a. Furthermore, this was observed to undergo rearrangement during analysis using gas chromatography-mass spectrometry (GC-MS) with products including 3-(2-chloroethyl)indole 3 and 2-methyltetrahydro-beta-carboline 4 (2-Me-THBC). This study further investigates this so far unexplored area of solvent interactions by the exposure of DMT to other halogenated solvents including dibromomethane and 1,2-dichloroethane (DCE). The N-bromomethyl- and N-chloroethyl quaternary ammonium derivatives were subsequently characterised by ion trap GC-MS in electron and chemical ionisation tandem MS mode and by NMR spectroscopy. The DCE-derived derivative formed at least six rearrangement products in the total ion chromatogram. Identification of mass spectrometry generated by-products was verified by conventional or microwave-accelerated synthesis. The use of deuterated DCM and deuterated DMT 1b provided insights into the mechanism of the rearrangements. The presence of potentially characteristic marker molecules may allow the identification of solvents used during the manufacture of controlled substances, which is often neglected since these are considered inert.