title: Mass spectrometric properties of N-(2-methoxybenzyl)-2-(2,4,6-trimethoxyphenyl)ethanamine (2,4,6-TMPEA-NBOMe), a new representative of designer drugs of NBOMe series and derivatives thereof.
abstract: Emergence of new psychoactive substances, hallucinogenic phenethylamines in particular, in illicit market is a serious threat to human health in global scale. We have detected and identified N-(2-methoxybenzyl)-2-(2,4,6-trimethoxyphenyl)ethanamine (2,4,6-TMPEA-NBOMe), a new compound in NBOMe series. Identification was achieved by means of gas chromatography/mass spectrometry (GC/MS), including high-resolution mass spectrometry with tandem experiments (GC/HRMS and GC/HRMS2), ultra-high performance liquid chromatography/high-resolution mass spectrometry with tandem experiments (UHPLC/HRMS and UHPLC/HRMS2), and1H and13C nuclear magnetic resonance spectroscopy. The peculiarities of fragmentation of the compound under electron ionization (EI) and collision-induced dissociation were studied. Despite of the empirical rule denying migration of the hydrogen atom in McLafferty rearrangement to the benzene ring with substituents in the both ortho-positions, it easily occurs for 2,4,6-TMPEA-NBOMe in EI conditions. We have noticed that electron-donating substituents, e.g. methoxy groups in the both ortho-positions and para-positions favor the rearrangement. For specially synthesized N-methyl and N-acyl derivatives McLafferty rearrangement is not observed. N-Acyl derivatives demonstrate McLafferty rearrangement, but the charge retains at the alternative fragment involving N-acyl carbonyl group. We have also showed that the hydrogen atoms in 2,4,6-trimethoxybenzene ring may be easily substituted for deuterium or for strong electrophiles like trifluoroacetyl. Analytical characteristics of 2,4,6-TMPEA-NBOMe and of some derivatives thereof which enable their determination in various criminal seizures are given. Copyright © 2016 John Wiley & Sons, Ltd.
authors.affiliation: Institute of Chemistry and Technology, Ural Federal University, 19 Mira St., Ekaterinburg, 620002, Russia. vadim.shevyrin@gmail.com.
authors.forename: Vadim
authors.identifier: http://orcid.org/0000-0002-0369-0786
authors.initials: V
authors.lastname: Shevyrin
authors.affiliation: Kazan Scientific Center, A.E. Arbuzov Institute of Organic and Physical Chemistry, Russian Academy of Sciences, 8 Arbuzov St., Kazan, 420088, Russia.
authors.forename: Olga
authors.initials: O
authors.lastname: Kupriyanova
authors.affiliation: Organic Chemistry Department, Lomonosov Moscow State University, Leninskie Gory 1/3, Moscow, 119991, Russia.
authors.forename: Albert T
authors.initials: AT
authors.lastname: Lebedev
authors.affiliation: Main Agency of the Ministry of the Interior of the Russian Federation, Sverdlovsk Region Branch, Expert and Criminalistic Center, 17 Lenina Avenue, Ekaterinburg, 620014, Russia.
authors.forename: Vladimir
authors.initials: V
authors.lastname: Melkozerov
authors.affiliation: Institute of Chemistry and Technology, Ural Federal University, 19 Mira St., Ekaterinburg, 620002, Russia.
authors.forename: Oleg
authors.initials: O
authors.lastname: Eltsov
authors.affiliation: Institute of Chemistry and Technology, Ural Federal University, 19 Mira St., Ekaterinburg, 620002, Russia.
authors.forename: Yuri
authors.initials: Y
authors.lastname: Shafran
authors.affiliation: Institute of Chemistry and Technology, Ural Federal University, 19 Mira St., Ekaterinburg, 620002, Russia.
authors.forename: Yuri
authors.initials: Y
authors.lastname: Morzherin
authors.affiliation: Kazan State Medical University, 49 Butlerov St., Kazan, 420012, Russia.
authors.forename: Raziya
authors.initials: R
authors.lastname: Sadykova
mesh_terms: D002851:Chromatography, High Pressure Liquid; D015198:Designer Drugs / Q000737:chemistry*; D003903:Deuterium; D008401:Gas Chromatography-Mass Spectrometry; D006801:Humans; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D010627:Phenethylamines / Q000737:chemistry / Q000494:pharmacology*; D021241:Spectrometry, Mass, Electrospray Ionization; D053719:Tandem Mass Spectrometry
chemical_list: D015198:Designer Drugs; C000626712:N-(2-methoxybenzyl)-2-(2,4,6-trimethoxyphenyl)ethanamine; D010627:Phenethylamines; D003903:Deuterium
keywords: McLafferty rearrangement; NBOMe; electrophilic substitution; high-resolution mass spectrometry; psychoactive substances