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Characterization and analysis of structural isomers of dimethyl methoxypyrazines in cork stoppers and ladybugs (Harmonia axyridis and Coccinella septempunctata)

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An Erratum to this article was published on 17 September 2014

Abstract

The three constitutional isomers of dimethyl-substituted methoxypyrazines: 3,5-dimethyl-2-methoxypyrazine 1; 2,5-dimethyl-3-methoxypyrazine 2; and 2,3-dimethyl-5-methoxypyrazine 3 are potent flavor compounds with similar mass spectrometric, gas chromatographic, and nuclear magnetic resonance spectroscopic behavior. Therefore, unambiguous analytical determination is critical, particularly in complex matrices. The unequivocal identification of 1–3 could be achieved by homo- and heteronuclear NMR correlation experiments. The observed mass fragmentation for 1–3 is proposed and discussed, benefitting from synthesized partially deuterated 1 and 2. On common polar and apolar stationary phases used in gas chromatography (GC) 1 and 2 show similar behavior whereas 3 can be separated. In our focus on off-flavor analysis with respect to wine aroma, 1 has been described as a “moldy” off-flavor compound in cork and 2 as a constituent in Harmonia axyridis contributing to the so-called “ladybug taint,” whereas 3 has not yet been described as a constituent of wine aroma. A successful separation of 1 and 2 could be achieved on octakis-(2,3-di-O-pentyl-6-O-methyl)-γ-cyclodextrin as stationary phase in GC. Applying heart-cut multidimensional GC analysis with tandem mass spectrometric detection we could confirm the presence of 1 as a “moldy” off-flavor compound in cork. However, in the case of Harmonia axyridis, a previous identification of 2 has to be reconsidered. In our experiments we identified the constitutional isomer 1, which was also found in Coccinella septempunctata, another species discussed with respect to the “ladybug taint.” The analysis of such structurally related compounds is a demonstrative example for the importance of a chromatographic separation, as mass spectrometric data by itself could not guarantee the unequivocal identification.

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Acknowledgements

We appreciate the financial support from the Ministerium für Umwelt, Landwirtschaft, Ernährung, Weinbau und Forsten (MULEWF; Rheinland-Pfalz, Germany). C. Legrum is grateful to the “Graduiertenförderung des Landes Rheinland-Pfalz” for a Ph.D. scholarship. We also like to thank Prof. Dr. Stefan Schulz (Institute for Organic Chemistry, Technical University of Braunschweig, Germany) for his suggestion on using a Meerwein salt for the selective O-alkylation of the intermediate compound 6. The authors are thankful to Supelco (Sigma-Aldrich) for the supply of SPME fibers.

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Authors and Affiliations

  1. Dienstleistungszentrum Ländlicher Raum (DLR) Rheinpfalz, Competence Center for Wine Research, Breitenweg 71, 67435, Neustadt an der Weinstraße, Germany

    Petra Slabizki, Charlotte Legrum & Hans-Georg Schmarr

  2. Faculty of Food Chemistry and Toxicology, Technical University of Kaiserslautern, Erwin-Schrödinger-Straße 52, 67663, Kaiserslautern, Germany

    Charlotte Legrum

  3. Institute of Organic Chemistry and Biochemistry, University of Technology Darmstadt, Alarich-Weiss-Str. 4, 64287, Darmstadt, Germany

    Reinhard Meusinger

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  1. Petra Slabizki
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  2. Charlotte Legrum
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  3. Reinhard Meusinger
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  4. Hans-Georg Schmarr
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Correspondence to Hans-Georg Schmarr.

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Peter Slabizki, Charlotte Legrum, and Reinhard Meusinger contributed equally to this work.

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Slabizki, P., Legrum, C., Meusinger, R. et al. Characterization and analysis of structural isomers of dimethyl methoxypyrazines in cork stoppers and ladybugs (Harmonia axyridis and Coccinella septempunctata). Anal Bioanal Chem 406, 6429–6439 (2014). https://doi.org/10.1007/s00216-014-8049-4

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