Tandem high-resolution electrospray ionization mass spectrometry of fluorinated thevinols and 18,19-dihydrothevinols

• Published in: Journal of analytical chemistry (New York, N.Y.) Vol. 70; no. 13; pp. 1561 - 1568
• Main Authors: Eremin, D. B, Kadentsev, V. I, Sandulenko, I. V, Moiseev, S. K
• Format: Journal Article
• Language: English
• Published: Moscow Pleiades Publishing 15-12-2015; Springer
• Subjects: Analytical Chemistry; Chemical properties; Chemical reactions; Chemistry; Chemistry and Materials Science; dissociation; electrospray ionization mass spectrometry; hydrogen; Identification and classification; ionization; ions; Mass spectrometry; methanol; Methods; nitrogen; Observations; Opioids; tandem mass spectrometry; retro-Diels–Alder fragmentation; thevinols; accurate mass; electrospray ionization; collisionally activated dissociation; dihydrothevinols
• ISSN: 1061-9348; 1608-3199
• DOI: 10.1134/S1061934815130031

Fragmentation of fluorinated 18,19-dihydrothevinols and thevinols under electrospray ionization with collisionally activated dissociation accompanied by the elimination of an amine fragment from the cycle and the subsequent loss of H₂O and CH₃OH have been studied. For thevinol derivatives with a double bond at C¹⁸=C¹⁹, the [M + H]⁺ ions undergo the retro-Diels–Alder fragmentation, the abundance of which depends on substituents at the nitrogen and C²⁰ atoms. The retro-Diels–Alder fragmentation of the [M + H]⁺ ions of thevinols bearing–CH₃,–CH₂CH=CH₂, and [Formula: see text] groups at the nitrogen atom occurs due to the formation of a protonated diene molecule, whereas the elimination of a neutral diene in thevinols with hydrogen at the nitrogen atom has been observed.