Unidirectional triple hydrogen rearrangement in the radical cations of electron-rich 3-aryl-1-propanols: further evidence and limitation

Kuck D, Salameh LC, Onwuka KI, Letzel M (2014)
European Journal of Mass Spectrometry 20(1): 51-61.

Zeitschriftenaufsatz | Veröffentlicht | Englisch
 
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Autor*in
Kuck, DietmarUniBi; Salameh, Linda C.; Onwuka, Kenneth I.; Letzel, MatthiasUniBi
Abstract / Bemerkung
The unidirectional triple-hydrogen (3H) rearrangement of the radical cations of 3-aryl-1-propanols bearing an electron-rich substitutent in the para-position was investigated for the diastereomeric 2-(4-dimethylamino)benzylcyclohexanols and 2-(4-dimethylamino)benzylcyclopentanols and confirmed to be a highly stereospecific feature. Whereas the standard electron ionization (EI) (70 eV) mass spectra of the trans-isomers exhibit very minor (-2%-3%) albeit stereospecific peaks for the relevant C8H13N center dot+ ions (m/z 123), the metastable ion [mass-analyzed ion kinetic energy (MIKE)] spectra show these peaks with significant relative intensity (8%-17%). The respective cis-isomers do not undergo the 3H rearrangement, be it under standard or under metastable-ion conditions. The stereospecific 3H rearrangement is suppressed in the radical cations of cis- and trans-3-(4-dimethylamino)phenylcyclohexanol, the mass and MIKE spectra of which are governed by cleavage processes of the cyclohexane ring, which impedes the stereochemical assignment of the isomers by mass spectrometry. A multistep mechanism for the unidirectional 3H rearrangement is discussed in view of the present and previous experimental data.
Stichworte
cycloalkanols; stereospecific fragmentation; anilines; stereochemistry; multistep reactions; metastable ions; radical cations; ion/neutral complexes; distonic ions; proton transfer; hydrogen rearrangement "triple"; "unidirectional"; hydrogen rearrangement
Erscheinungsjahr
2014
Zeitschriftentitel
European Journal of Mass Spectrometry
Band
20
Ausgabe
1
Seite(n)
51-61
ISSN
1356-1049
Page URI
https://pub.uni-bielefeld.de/record/2677434

Zitieren

Kuck D, Salameh LC, Onwuka KI, Letzel M. Unidirectional triple hydrogen rearrangement in the radical cations of electron-rich 3-aryl-1-propanols: further evidence and limitation. European Journal of Mass Spectrometry. 2014;20(1):51-61.
Kuck, D., Salameh, L. C., Onwuka, K. I., & Letzel, M. (2014). Unidirectional triple hydrogen rearrangement in the radical cations of electron-rich 3-aryl-1-propanols: further evidence and limitation. European Journal of Mass Spectrometry, 20(1), 51-61. doi:10.1255/ejms.1239
Kuck, D., Salameh, L. C., Onwuka, K. I., and Letzel, M. (2014). Unidirectional triple hydrogen rearrangement in the radical cations of electron-rich 3-aryl-1-propanols: further evidence and limitation. European Journal of Mass Spectrometry 20, 51-61.
Kuck, D., et al., 2014. Unidirectional triple hydrogen rearrangement in the radical cations of electron-rich 3-aryl-1-propanols: further evidence and limitation. European Journal of Mass Spectrometry, 20(1), p 51-61.
D. Kuck, et al., “Unidirectional triple hydrogen rearrangement in the radical cations of electron-rich 3-aryl-1-propanols: further evidence and limitation”, European Journal of Mass Spectrometry, vol. 20, 2014, pp. 51-61.
Kuck, D., Salameh, L.C., Onwuka, K.I., Letzel, M.: Unidirectional triple hydrogen rearrangement in the radical cations of electron-rich 3-aryl-1-propanols: further evidence and limitation. European Journal of Mass Spectrometry. 20, 51-61 (2014).
Kuck, Dietmar, Salameh, Linda C., Onwuka, Kenneth I., and Letzel, Matthias. “Unidirectional triple hydrogen rearrangement in the radical cations of electron-rich 3-aryl-1-propanols: further evidence and limitation”. European Journal of Mass Spectrometry 20.1 (2014): 51-61.

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