Electrochemical mass spectrometric studies on 1‐cyclopropyl‐4‐phenyl‐1,2,3,6‐tetrahydropyridine

Abstract

Mechanistic studies on chemical and biological one-electron oxidations of cyclic tertiary allylamines are being pursued with the aid of an electrochemical-electrospray ionization mass spectrometric based assay. The results of previous studies on the electrochemical oxidation of 1-cyclopropyl-4-phenyl-1,2,3,6-tetrahydropyridine have documented a two-electron oxidative N-decyclopropylation pathway. The present paper describes the characterization of a second pathway involving an overall four-electron oxidation of this cyclopropylamine. The results document more completely the fate of cyclopropylaminyl radical cations that are thought to be intermediates in enzyme-catalyzed oxidations of aminyl substrates and that may lead to chemically reactive metabolites.

Electrochemical Aspects of Mass Spectrometry: Atmospheric Pressure Ionization and Ambient Ionization for Bioanalysis

“…For instance, mass voltammograms were used to understand breakdown of Gd‐based contrast agents, which are used for magnetic resonance imaging, by observation of oxidative metabolites . Further, mass voltammograms were employed to screen antibacterial agents in personal care products for possible environmental pollutants and to elucidate pathways for breakdown of 1‐methyl‐4‐phenyl‐1,2,3,6‐tetrahydropyridine, a neurotoxic ‘street drug’ known as MPTP, in addition to many more possibilities. Oxidation processes of nucleic acids have important biological implications for cell mutation, aging, and death.…”

Electrosynthesis methods and approaches for the preparative production of metabolites from parent drugs

“…On-line sampling is also possible in a batch cell (Fig. 4a), but solution compatibility with ESI-MS becomes an issue again [70].…”

Recent advances of electrochemical mass spectrometry

“…In addition, a complete 4-electron oxidation pathway (Scheme 2, bottom row) was further proposed, based on the observation of a water-derived intermediate 14 in the oxidation of 1-cyclopropyl-4-phenyl-1,2,3,6-tetrahydropyridine, providing more insight into the oxidation reaction. 87 Additional applications of EC/ESI-MS to the investigation of the redox pathways of organic compounds including PAHs, amines, alcohols, thiolates, nitroaromatics, neurotransmitters, organometallics or the reaction intermediates are summarized in Table 1.…”