title: N,N-Dimethyltryptamine and dichloromethane: rearrangement of quaternary ammonium salt product during GC-EI and CI-MS-MS analysis.
abstract: N,N-Dimethyltryptamine (DMT) 1 is a simple tryptamine derivative with powerful psychoactive properties. It is abundant in nature and easily accessible through a variety of synthetic routes. Most work-up procedures require the use of organic solvents and halogenated representatives are often employed. DMT was found to be reactive towards dichloromethane, either during work-up or long term storage therein, which led to the formation of the quaternary ammonium salt N-chloromethyl-DMT chloride 2. Analysis of this side-product by gas chromatography ion trap mass spectrometry (GC-MS), both in electron and chemical ionisation tandem MS modes, gave only degradation products. For example, 2 could not be detected but appeared to have rearranged to 3-(2-chloroethyl)indole 3 and 2-methyltetrahydro-beta-carboline 4, whereas HPLC analysis enabled the detection of 2. GC-MS is a standard tool for the fingerprinting of drug products. The identification of a particular synthetic route is based on the analysis of impurities, provided these side products can be established to be route-specific. The in situ detection of both 3 and 4 within a DMT sample may have led to erroneous conclusions with regards to the identification of the synthetic route.
authors.affiliation: School of Pharmacy and Chemistry, Liverpool John Moores University, Byrom Street, Liverpool, L3 3AF, UK. s.brandt@ljmu.ac.uk
authors.forename: Simon D
authors.initials: SD
authors.lastname: Brandt
authors.forename: Cláudia P B
authors.initials: CP
authors.lastname: Martins
authors.forename: Sally
authors.initials: S
authors.lastname: Freeman
authors.forename: Nicola
authors.initials: N
authors.lastname: Dempster
authors.forename: Mark
authors.initials: M
authors.lastname: Wainwright
authors.forename: Philip G
authors.initials: PG
authors.lastname: Riby
authors.forename: John F
authors.initials: JF
authors.lastname: Alder
mesh_terms: D008401:Gas Chromatography-Mass Spectrometry / Q000379:methods*; D008752:Methylene Chloride / Q000032:analysis* / Q000737:chemistry; D004130:N,N-Dimethyltryptamine / Q000032:analysis* / Q000737:chemistry; D000644:Quaternary Ammonium Compounds / Q000737:chemistry*
chemical_list: D000644:Quaternary Ammonium Compounds; D008752:Methylene Chloride; D004130:N,N-Dimethyltryptamine