Objective: To explore the fragmentation patterns of synthetic cannabinoids by electron impact (EI) ionization mass spectrometry. Methods: Forty synthetic cannabinoids were systematically investigated by gas chromatography coupled to mass spectrometry (GC-MS). Ionization mode was EI (70 eV) and the acquisition range was m/z 50-600. Results: According to the different structures of the “head group” and “linked group”, forty synthetic cannabinoids were divided into six categories, namely cumyl-carboxamide type, adamantyl-carboxamide type, carbamoyl/methyl butyrate-carboxamide type, naphthylformyl type, benzoyl/phenylacetyl type and tetramethylcyclopropane-acyl type. Through the analysis of the mass spectrum of synthetic cannabinoids, the fragmentation pathways and characteristic ions of different types of synthetic cannabinoids were given. The main EI-MS fragmentation patterns of synthetic cannabinoids were that both sides of the carbonyl group in the “linking group” undergo α-cleavage, and the N atom on the indole/indazole parent nucleus was prone to γ-H rearrangement, and loss of a R1. In addition, fragment ions m/z 116, 130, 144 and fragment ions m/z 117, 131, 145 were the characteristic fragments of indazole and indole parent nucleus, which could be used to identify the parent nucleus of synthetic cannabinoids. Conclusion: These kind of compounds have strong fragmentation regularity. When standard substances are lacking or commercial mass spectral libraries are difficult to obtain, the proposed synthetic cannabinoids EI-MS fragmentation pathways can help to rapidly identify the structures of unknown synthetic cannabinoids.
Key words
synthetic cannabinoids /
GC-MS /
electron impact ionization tandem mass spectrometry /
structural classification /
fragmentation patterns /
characteristic fragmentation ion
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Footnotes
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