1. Crystallographic characterization of three cathinone hydrochlorides new on the NPS market: 1-(4-methylphenyl)-2-(pyrrolidin-1-yl)hexan-1-one (4-MPHP), 4-methyl-1-phenyl-2-(pyrrolidin-1-yl)pentan-1-one (α-PiHP) and 2-(methylamino)-1-(4-methylphenyl)pentan-1-one (4-MPD)
Marcin Rojkiewicz, Piotr Kuś, Maria Książek, Joachim Kusz Acta Crystallogr C Struct Chem. 2022 Jan 1;78(Pt 1):56-62. doi: 10.1107/S2053229621013401. Epub 2022 Jan 1.
Cathinones belong to a group of compounds of great interest in the new psychoactive substances (NPS) market. Constant changes to the chemical structure made by the producers of these compounds require a quick reaction from analytical laboratories in ascertaining their characteristics. In this article, three cathinone derivatives were characterized by X-ray crystallography. The investigated compounds were confirmed as: 1-[1-(4-methylphenyl)-1-oxohexan-2-yl]pyrrolidin-1-ium chloride (1, C17H26NO+·Cl-, the hydrochloride of 4-MPHP), 1-(4-methyl-1-oxo-1-phenylpentan-2-yl)pyrrolidin-1-ium chloride (2; C16H24NO+·Cl-, the hydrochloride of α-PiHP) and methyl[1-(4-methylphenyl)-1-oxopentan-2-yl]azanium chloride (3; C13H20NO+·Cl-, the hydrochloride of 4-MPD). All the salts crystallize in a monoclinic space group: 1 and 2 in P21/c, and 3 in P21/n. To the best of our knowledge, this study provides the first detailed and comprehensive crystallographic data on salts 1-3.
2. Mixed Macrocycles Derived from 2,6-Diformylpyridine and Opposite Enantiomers of trans-1,2-Diaminocyclopentane and trans-1,2-Diaminocyclohexane
Rafał Frydrych, Katarzyna Ślepokura, Andrzej Bil, Janusz Gregoliński J Org Chem. 2019 May 3;84(9):5695-5711. doi: 10.1021/acs.joc.9b00614. Epub 2019 Apr 22.
The condensation reaction of 2,6-diformylpyridine with an equimolar mixture of opposite enantiomers of trans-1,2-diaminocyclopentane and trans-1,2-diaminocyclohexane using a dynamic combinatorial chemistry approach has been examined. In nonmetal-templated reactions, depending on reaction conditions, mixed 2 + 1 + 1 macrocyclic imine or bigger mixed 4 + 2 + 2 imine macrocycle are formed selectively. The 2 + 1 + 1 imine used as a precursor in the templated by CdII ions produces a library of enlarged chiral mixed imines coordinated with metal cations among which the hexanuclear CdII complex of 6 + 3 + 3 imine was isolated and characterized. All macrocyclic imine compounds have been reduced to the corresponding macrocyclic amines, which have been further transformed into their hydrochlorides. Each macrocyclic compound has been obtained as two enantiomers. For imine macrocycles and for the hydrochloride derivatives of macrocyclic amines, their X-ray crystal structures have been determined. In particular, the crystals of protonated 4 + 2 + 2 macrocyclic amine, which contains two types of diastereomeric cations differing in terms of inverted twists of pyridine moieties, and hexanuclear CdII complex of 6 + 3 + 3 imine, which gives a deeper insight into the expansion reaction, have been investigated. A heterochiral self-sorting of 2 + 2 and 2 + 1 + 1 macrocyclic imines has been confirmed by a competition reaction of 2,6-diformylpyridine, racemic trans-1,2-diaminocyclopentane, and racemic trans-1,2-diaminocyclohexane and theoretical calculations.
