The thermodynamic study of morpholinium 2-((4-(2-methoxyphenyl)-5-(pyridinyl)-4H-1,2,4-triazol-3-yl)thio)acetate and its technological impurities in hydrophilic chromatography

Authors

DOI:

https://doi.org/10.24959/ophcj.20.209776

Keywords:

thermodynamic characteristics, hydrophilic liquid chromatography, 1, 2, 4-triazole derivatives

Abstract

Aim. To study the dependence of the retention of morpholinium 2-((4-(2-methoxyphenyl)-5-(pyridinyl)-4H-1,2,4-triazol-3-yl)thio)acetate and its technological impurities on temperature, as well as determine the thermodynamic characteristics of the transfer from the mobile phase to the stationary phase using hydrophilic chromatography.

Results and discussion. The retention factors depending on the absolute temperature were determined in order to study the thermodynamic parameters of the transfer of analytes from the mobile phase to the stationary one. Based on the van ‘t Hoff equation a curve of lnk dependence on 1/T was constructed. The least squares method was used to create the linear dependence equation. The standard molar enthalpies, as well as the conditional standard entropy of the transfer from the mobile to the stationary phase of the test substances, namely morpholinium 2-((4-(2-methoxyphenyl)-5-(pyridinyl)-4H-1,2,4-triazol-3-yl)thio)acetate, pyridine-4-carbohydrazide, 2-isonicotinoyl-N-(2-methoxyphenyl)hydrazine-1-carbothioamide and 4-(2-methoxyphenyl)-5-(pyridinyl)-2,4-dihydro-3H-1,2,4-triazole-3-thione were calculated. The negative enthalpy of the transfer for all substances shows that the substances are adsorbed on the surface of a silica gel with the release of heat. Therefore, the process of transition of a substance from the mobile phase to the stationary one prevails over the reverse process.

Experimental part. The Agilent 1260 Infinity liquid chromatography system consisting of a degasser, binary pump, autosampler, column thermostat, diode array detector was used for our experiments.

Conclusions. It has been found that all the compounds studied have a negative value of the transfer enthalpy, and it indicates the predominant transition of these analytes from the mobile phase to the stationary one. Conditional standard entropies of the analyte transfer from the mobile phase to the stationary phase have been calculated, and it has been proven that they significantly affect the transfer process.

Received: 11.08.2020
Revised: 25.10.2020
Accepted: 14.11.2020

Supporting Agencies

  • The theme of Ministry of Health of Ukraine «The development of procedures of analysis and the investigation of 1
  • 2
  • 4-triazole derivatives as potential active pharmaceutical ingredients using HPLC» (№0120U101650
  • 2020 – 2022 years)

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References

  1. Kaplaushenko, A. G. Synthesis, physicochemical and biological properties of S-derivatives of 5-(2-, 3-, 4-nitrophenyl)-1,2,4-triazol-3-thiones. Ph.D. Thesis, Shupyk National Medical Academy of Postgraduate Education, Kyiv, 2006.
  2. Kaplaushenko, A. G. Synthesis Methods and Biological Activity of 1,2,4-Triazol-3-thions. Ukrainian biopharmaceutical journal 2009, 1 (4), 48 – 56.
  3. Kaplaushenko, A. G. Synthesis, structure and biological activity of 4-mono-and 4,5-disubstituted 1,2,4-triazole-3-one derivatives. D.Sc. Thesis, Zaporizhzhya State Medical University, Zaporizhzhya, 2012.
  4. Varynskyi, B.; Kaplaushenko, A. Metabolism study of morpholinium 2-((4-(2-methoxyphenyl)-5-(pyridin-4-yl)-4H-1,2,4-triazole-3-yl)thio)acetate. Current Issues in Pharmacy and Medical Sciences 2020, 33 (2), 72 – 75. https://doi.org/10.2478/cipms-2020-0014.
  5. Linford, M. R.; Clark, J.; Teutenberg, Th. Elevated Temperatures in Liquid Chromatography, Part I: Benefits and Practical Considerations. LCGC Europe 2013, 26 (2), 78 – 85.
  6. Linford, M. R.; Jensen, D. S.; Clark, J.; Teutenberg, Th. Elevated Temperatures in Liquid Chromatography, Part II: Basic Thermodynamics of Elevated Temperature LC, Including the van ‘t Hoff Relationship. LCGC North America 2012, 30 (11), 992 – 998.
  7. Linford, M. R.; Jensen, D. S.; Clark, J.; Teutenberg, Th. Elevated Temperatures in Liquid Chromatography, Part III: A Closer Look at the van ‘t Hoff Equation. LCGC North America 2012, 30 (12), 1052 – 1057.
  8. Rane, V. P.; Ahirrao, V. K.; Patil, K. R.; Jadhav, R. A.; Ingle, R. G.; More, K. B.; Yeole, R. D. Enantiomeric Separation and Thermodynamic investigation of (R)-5-[1-(4-Nitrobenzylsulfonyloxy)-ethyl]-5-(pyridine-2-yl)-[1,3,4]-thiadiazole, a Key Intermediate of Nafithromycin. Analytical Chemistry
  9. Letters 2019, 9 (5), 625 – 633. https://doi.org/10.1080/22297928.2019.1694433.
  10. Zhang, L.; Hu, Y.; Galella, E.; Tomasella, F. P.; Fish, W. P. Separation of atropisomers by chiral liquid chromatography and thermodynamic analysis of separation mechanism. Journal of Pharmaceutical Analysis 2017, 7 (3), 156 – 162. https://doi.org/10.1016/j.jpha.2017.03.003.
  11. Dungelová, J.; Lehotay, J.; Krupčík, J.; Cižmárik, J.; Armstrong, D. W. Study of the mechanism of enantioseparation Part VI: Thermodynamic study of HPLC separation of some enantiomers of phenylcarbamic acid derivatives on a (S,S) Whelk-O 1 column. J. Sep. Sci. 2004, 27 (12), 983 – 990.
  12. https://doi.org/10.1002/jssc.200301591.
  13. Hales, T. C. An overview of the Kepler conjecture. https://arxiv.org/pdf/math/9811071.pdf (accessed Nov 11, 2020).

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Published

2020-12-01

How to Cite

(1)
Varynskyi, B. O. The Thermodynamic Study of Morpholinium 2-(4-(2-Methoxyphenyl)-5-(pyridinyl)-4H-1,2,4-Triazol-3-yl)thio)acetate and Its Technological Impurities in Hydrophilic Chromatography. J. Org. Pharm. Chem. 2020, 18, 50-55.

Issue

Vol. 18 No. 4(72) (2020)

Section

Original Researches

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