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Understanding the Formation of 5-(Diethylammoniothio)-1,3-dimethylbarbituric Acid: Crystal Structure and DFT Studies

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Abstract

5-(Diethylammoniothio)-1,3-dimethylbarbituric acid (8) was obtained in good yield from the reaction of 5-bromo-1,3-dimethylbarbituric acid (5) and 1,3-diethylthiourea. The obtained product has been characterized using different techniques including single-crystal X-ray diffraction, FTIR, MS and NMR spectroscopy. For this reaction, a detailed computational study of the reaction steps has been performed using density functional theory (DFT). Both thermodynamic and kinetic parameters were calculated. Step B is the most favorable reaction with an activation energy of 33 kJ mol−1 using the solvation model that based on the solvent model density (SMD) calculated at B3LYP/6-31G(d).

Graphic abstract

The rate-determining step of the most plausible mechanism involves the formation of C-S bond via proton transfer to oxygen (intramolecular attraction) with an activation barrier of 33 kJ mol-1 using the solvation model that based on density (SMD) solvent model calculated at B3LYP/6-31G(d).

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Authors and Affiliations

  1. Department of Chemistry, School of Science, The University of Jordan, Amman, 11942, Jordan

    Kamal Sweidan, Mansour H. Almatarneh, Murad A. AlDamen, Monther Khanfar & Reema A. Omeir

  2. Department of Chemistry, Memorial University, St. John’s, NL, A1B 3X7, Canada

    Mansour H. Almatarneh

  3. Institut für Anorganische Chemie der Universität Tübingen, Auf der Morgenstelle 18, 72076, Tübingen, Germany

    Caecilia Maichle Mössmer & Manfred Steimann

Authors
  1. Kamal Sweidan
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  2. Mansour H. Almatarneh
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  3. Murad A. AlDamen
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  4. Monther Khanfar
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  5. Reema A. Omeir
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  6. Caecilia Maichle Mössmer
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  7. Manfred Steimann
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Correspondence to Mansour H. Almatarneh or Murad A. AlDamen.

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10870_2020_846_MOESM1_ESM.docx

Additional Supporting Information may be found online in the supporting information tab for this article. X-ray crystallographic data for the structural analyses have been deposited with the Cambridge Crystallographic Data Centre (compound 8: CCDC No. 1981657). Potential energy diagram for steps A and B along with the Cartesians coordinates for all stationary points for proposed mechanisms and thermochemical data. CIF files containing complete information on the studied structures may be obtained free of charge from the Director, CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK, Fax 0044-1223- 336033; E-mail:deposit@ccdc.cam.ac.uk or from the following web site: www.ccdc.cam.ac.uk/data_request/cif. Supplementary file1 (DOCX 1017 kb)

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Sweidan, K., Almatarneh, M.H., AlDamen, M.A. et al. Understanding the Formation of 5-(Diethylammoniothio)-1,3-dimethylbarbituric Acid: Crystal Structure and DFT Studies. J Chem Crystallogr 51, 215–224 (2021). https://doi.org/10.1007/s10870-020-00846-1

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  • DOI: https://doi.org/10.1007/s10870-020-00846-1

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