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Protonation of Chelidamic Acid: Thermodynamic Analysis and Crystal Structure

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Abstract

Thermodynamics of the protonation of chelidamic acid (4-oxo-1,4-dihydropyridine-2,6-dicarboxylic acid) was studied using potentiometry and calorimetry in 0.1 mol·L− 1 NaClO4 solution at 298 K under standard pressure (p = 0.1 MPa). There are three successive protonation steps. The protonation constants of each step (log10K) are calculated as 10.74 ± 0.01, 3.22 ± 0.02, and 1.63 ± 0.03. The first two protonation steps are exothermic, while the last step is endothermic. All the protonation steps are mainly driven by entropy. The three protonation states (HL2−, H2L− and H3L) were analyzed using the 1 H NMR spectra and crystal structure. The results confirm that the order of successive protonation sites is the pyridine-N (HL2−), pyridinol-OH (H2L−), and carboxylate oxygen atom (H3L).

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Acknowledgements

This work is supported by the National Natural Science Foundation of China (Grant No. 21976165, 22076175, 22006141, and U1830202).

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Authors and Affiliations

  1. Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mail stop 919-216, 64 Mianshan Road, 621999, Mianyang, Sichuan, China

    Baihua Chen, Wanjun Mu, Yuchuan Yang, Bijun Liu, Yanqiu Yang, Hongyuan Wei, Shuming Peng & Xingliang Li

  2. School of Biotechnology and Health Sciences, Wuyi University, 529020, Jiangmen, Guangdong, China

    Juncai Lu

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  1. Baihua Chen
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Chen, B., Lu, J., Mu, W. et al. Protonation of Chelidamic Acid: Thermodynamic Analysis and Crystal Structure. J Solution Chem 51, 1187–1198 (2022). https://doi.org/10.1007/s10953-022-01164-0

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