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Synthesis and crystal structures of two isomeric nitro-α-resorcylic acids

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Abstract

Nitration of α-resorcylic acid (3,5-dihydroxybenzoic acid) to 3,5-dihydroxy-2-nitrobenzoic acid (1) and 3,5-dihydroxy-4-nitrobenzoic acid (2), their separation, and crystallization is described. Crystal structures of 1, 1 · 3H2O, and 2 were determined by X-ray single-crystal diffraction analysis and compared with DFT-calculated structures. An intramolecular hydrogen bond between the nitro group and o-hydroxyl group(s) occurs in all investigated structures. Intermolecular hydrogen bonds and π···π stacking interactions determine the molecular packing. Additionally, N···O interactions have a crucial role in arrangement of the molecules in the crystal structures of 1 and 2. DFT calculations in the gas phase and in the solution reveal that minor product 2 is a more stable regioisomer than 1, the major product in the nitration reaction.

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Acknowledgments

This research was supported by GlaxoSmithKline Research Centre Zagreb Ltd. and by the Ministry of Science, Education and Sports of the Republic of Croatia (Grant No. 119-1193079-1084).

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Authors and Affiliations

  1. Laboratory of Organic Chemistry, Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, Zagreb, Croatia

    Ilija Čorić

  2. Chemistry Department, GlaxoSmithKline Research Centre Zagreb Ltd., Prilaz Baruna Filipovića 29, Zagreb, Croatia

    Ilija Čorić & Linda Tomašković

  3. Laboratory of General and Inorganic Chemistry, Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, Zagreb, Croatia

    Dalibor Milić & Dubravka Matković-Čalogović

Authors
  1. Ilija Čorić
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  2. Dalibor Milić
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  3. Dubravka Matković-Čalogović
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  4. Linda Tomašković
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Correspondence to Ilija Čorić.

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Čorić, I., Milić, D., Matković-Čalogović, D. et al. Synthesis and crystal structures of two isomeric nitro-α-resorcylic acids. Struct Chem 20, 73–80 (2009). https://doi.org/10.1007/s11224-008-9394-8

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