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The unsubstituted ortho-amidino benzoic acid: crystal structure, characterization and pK a determination

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Abstract

The simplest o-amidino benzoic acid—2-(amino(imino)methyl)benzoic acid—has been isolated in 23 % yield as a side product of the reaction of phthalonitrile and ammonia along with desired 1-imino-1H-isoindol-3-amine. This amidino acid was fully characterized by nuclear magnetic resonance, IR spectroscopy, mass spectrometry; pKa values were also determined. X-ray diffraction study and quantum chemical calculations revealed that in the solid state it exists as a zwitterion that is stabilized by intermolecular hydrogen bonds.

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Acknowledgments

We thank Konstanz University for visiting professorship (to O. V. H.) and Dr. Nikolay Youhnovski for providing ESI mass spectrum measurements. We are grateful to Dr. Agnieszka Dobosz (Wroclaw Medical University, Poland) for carrying out pK a determination. We would like to thank Dr. Svetlana Shishkina for X-ray and computational discussion, and Dr. Andrei Esaulenko (ALSI-CHROM, Kyiv) for ESI–MS analysis discussion.

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Authors and Affiliations

  1. Department of Chemistry, Taras Shevchenko National University of Kyiv, 64/13 Volodymyrs’ka str., Kyiv, 01601, Ukraine

    Olga V. Hordiyenko, Angelina V. Biitseva, Yuliya Yu. Kostina & Mikhail Yu. Kornilov

  2. SSI “Institute for Single Crystals” National Academy of Science of Ukraine, 60 Lenina ave., Kharkiv, 61001, Ukraine

    Roman I. Zubatyuk & Oleg V. Shishkin

  3. Department of Inorganic Chemistry, V. N. Karazin Kharkiv National University, 4 Svobody sq., Kharkiv, 61122, Ukraine

    Oleg V. Shishkin

  4. Fachbereich Chemie, Universität Konstanz, 78457, Konstanz, Germany

    Ulrich M. Groth

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  1. Olga V. Hordiyenko
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  2. Angelina V. Biitseva
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  4. Roman I. Zubatyuk
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Correspondence to Olga V. Hordiyenko.

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Dedicated to the memory of Prof. Oleg V. Shishkin and Prof. Ulrich M. Groth.

Oleg V. Shishkin and Ulrich M. Groth: Deceased.

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Hordiyenko, O.V., Biitseva, A.V., Kostina, Y.Y. et al. The unsubstituted ortho-amidino benzoic acid: crystal structure, characterization and pK a determination. Struct Chem 28, 607–616 (2017). https://doi.org/10.1007/s11224-016-0822-x

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  • DOI: https://doi.org/10.1007/s11224-016-0822-x

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