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Use of electrospray ionization mass spectrometry for the investigation of radical cation chain reactions in solution: detection of transient radical cations

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Abstract

Electrospray ionization mass spectrometry (ESI-MS) coupled to a microreactor is an excellent tool for the investigation of reactions in solution. Here, we report the first results of our investigations into preparatively interesting electron-transfer-initiated chain reactions in solution which proceed via radical cations as reactive intermediates. The tris(p-bromophenyl)aminium hexachloroantimonate (1)-mediated [2+2] cycloaddition of trans-anethole (2) to give 1,2-bis(4-methoxyphenyl)-3,4-dimethylcyclobutane (3) was investigated. The reaction proceeds as a radical cation chain reaction via transient intermediates 2 ●+ and 3 ●+ that could be detected and characterized unambiguously directly in the reacting solution by ESI-MS/MS. The identity of the intermediates was confirmed by comparison with authentic MS/MS spectra of 2 ●+ and 3 ●+ obtained by atmospheric pressure chemical ionization mass spectrometry (APCI-MS). In addition, substrate and product can be monitored easily in the reacting solution by APCI-MS.

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Acknowledgements

We thank the German Research Association (DFG) and the Heinz Neumüller Foundation Oldenburg for financial support.

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Authors and Affiliations

  1. Department of Chemistry, Carl von Ossietzky University, Carl-von-Ossietzky-Str. 9–11, 26111, Oldenburg, Germany

    Sven Meyer & Jürgen O. Metzger

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  1. Sven Meyer
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  2. Jürgen O. Metzger
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Correspondence to Jürgen O. Metzger.

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Part of this work was presented at the 36th Conference of the German Society for Mass Spectrometry (DGMS).

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Meyer, S., Metzger, J.O. Use of electrospray ionization mass spectrometry for the investigation of radical cation chain reactions in solution: detection of transient radical cations. Anal Bioanal Chem 377, 1108–1114 (2003). https://doi.org/10.1007/s00216-003-2230-5

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  • DOI: https://doi.org/10.1007/s00216-003-2230-5

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