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Preparation of carboxylate derivatives of terpyridine via the furan pathway

Nature Protocols volume 9, pages 21–26 (2014)Cite this article

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Abstract

This protocol describes a practical procedure for the preparation of terpyridine carboxy derivatives, which have numerous applications, including being photoactive components of functional materials, and which can be used in medicinal chemistry or in catalysis. This protocol relies on the permanganate-mediated oxidation of a furan ring on the polypyridine system. The procedure involves three stages. First, a furan-functionalized terpyridine is synthesized from furfuraldehyde and a 2-acetylpyridine derivative. Second, the furan ring is oxidized thus providing a carboxylic acid. Finally, esters are prepared by reaction of the acids in refluxing alcohols. The procedure is simple, uses a reagent available from renewable resources (furfural) and avoids the use of noxious reagents or solvents, thus making it more environmentally friendly when compared with previously described methods. The whole protocol can be conducted in ∼10 d, including isolation and drying of intermediates and products.

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Figure 1
Figure 2
Figure 3: First stage of the protocol: preparation of furyl precursors 3 and 4.
Figure 4
Figure 5: Final stage of the protocol: esterification.
Figure 6: Other examples of furan oxidation on bipyridine and terpyridine complexes.

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Acknowledgements

Ville de Besançon is acknowledged for a doctoral grant to J.D. Université de Franche-Comté is acknowledged for financial support through project Bonus Qualité Recherche (BQR) Rebiocell. We would like to thank Dr. I. Jourdain for recording NMR spectra of compounds 7 and 8.

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Authors and Affiliations

  1. Institut Univers, Transport, Interfaces, Nanostructures, Atmosphère et environnement, Molécules (UTINAM), Unité Mixte de Recherche (UMR), Centre National de Recherche Scientifique (CNRS) 6213, Université de Franche-Comté, Besançon, France

    Jérôme Husson, Jérémy Dehaudt & Laurent Guyard

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  1. Jérôme Husson
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  3. Laurent Guyard
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Contributions

J.H. supervised the project, developed the protocol for compound 7, reproduced experiments for compound 8 and wrote the manuscript. J.D. developed the protocol for compound 8. L.G. supervised the project, recorded some analysis and brought assistance in manuscript writing.

Corresponding author

Correspondence to Jérôme Husson.

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The authors declare no competing financial interests.

Integrated supplementary information

Supplementary information

Supplementary Figure 1

Picture of TLC plate of compounds 7 and 8. (PDF 338 kb)

Supplementary Data 1

1H NMR spectrum of compound 7. (PDF 175 kb)

Supplementary Data 2

IR spectrum of compound 7. (PDF 338 kb)

Supplementary Data 3

1H NMR spectrum of compound 8. (PDF 169 kb)

Supplementary Data 4

IR spectrum of compound 8. (PDF 322 kb)

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Husson, J., Dehaudt, J. & Guyard, L. Preparation of carboxylate derivatives of terpyridine via the furan pathway. Nat Protoc 9, 21–26 (2014). https://doi.org/10.1038/nprot.2013.162

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