Catalytic Sulfation of Betulin with Sulfamic Acid: Experiment and DFT Calculation
Betulin is an important triterpenoid substance isolated from birch bark, which, together with its sulfates, exhibits important bioactive properties. We report on a newly developed method of betulin sulfation with sulfamic acid in pyridine in the presence of an Amberlyst<sup>®</sup>15 sol...
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MDPI AG
2022-01-01
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| Series: | International Journal of Molecular Sciences |
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| author | Aleksandr S. Kazachenko Feride Akman Natalya Yu. Vasilieva Noureddine Issaoui Yuriy N. Malyar Aleksandr A. Kondrasenko Valentina S. Borovkova Angelina V. Miroshnikova Anna S. Kazachenko Omar Al-Dossary Marek J. Wojcik Yaroslava D. Berezhnaya Evgeniy V. Elsuf’ev |
| author_facet | Aleksandr S. Kazachenko Feride Akman Natalya Yu. Vasilieva Noureddine Issaoui Yuriy N. Malyar Aleksandr A. Kondrasenko Valentina S. Borovkova Angelina V. Miroshnikova Anna S. Kazachenko Omar Al-Dossary Marek J. Wojcik Yaroslava D. Berezhnaya Evgeniy V. Elsuf’ev |
| author_sort | Aleksandr S. Kazachenko |
| collection | DOAJ |
| description | Betulin is an important triterpenoid substance isolated from birch bark, which, together with its sulfates, exhibits important bioactive properties. We report on a newly developed method of betulin sulfation with sulfamic acid in pyridine in the presence of an Amberlyst<sup>®</sup>15 solid acid catalyst. It has been shown that this catalyst remains stable when being repeatedly (up to four cycles) used and ensures obtaining of sulfated betulin with a sulfur content of ~10%. The introduction of the sulfate group into the betulin molecule has been proven by Fourier-transform infrared, ultraviolet-visible, and nuclear magnetic resonance spectroscopy. The Fourier-transform infrared (FTIR) spectra contain absorption bands at 1249 and 835–841 cm<sup>−1</sup>; in the UV spectra, the peak intensity decreases; and, in the nuclear magnetic resonance (NMR) spectra, of betulin disulfate, carbons С3 and С28 are completely shifted to the weak-field region (to 88.21 and 67.32 ppm, respectively) with respect to betulin. Using the potentiometric titration method, the product of acidity constants K<sub>1</sub> and K<sub>2</sub> of a solution of the betulin disulfate H<sup>+</sup> form has been found to be 3.86 × 10<sup>–6</sup> ± 0.004. It has been demonstrated by the thermal analysis that betulin and the betulin disulfate sodium salt are stable at temperatures of up to 240 and 220 °C, respectively. The density functional theory method has been used to obtain data on the most stable conformations, molecular electrostatic potential, frontier molecular orbitals, and mulliken atomic charges of betulin and betulin disulfate and to calculate the spectral characteristics of initial and sulfated betulin, which agree well with the experimental data. |
| first_indexed | 2024-03-09T23:45:34Z |
| format | Article |
| id | doaj.art-3408b7bdc44c42fc8ebf34340c4acaac |
| institution | Directory Open Access Journal |
| issn | 1661-6596 1422-0067 |
| language | English |
| last_indexed | 2024-03-09T23:45:34Z |
| publishDate | 2022-01-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | International Journal of Molecular Sciences |
| spelling | doaj.art-3408b7bdc44c42fc8ebf34340c4acaac2023-11-23T16:43:17ZengMDPI AGInternational Journal of Molecular Sciences1661-65961422-00672022-01-01233160210.3390/ijms23031602Catalytic Sulfation of Betulin with Sulfamic Acid: Experiment and DFT CalculationAleksandr S. Kazachenko0Feride Akman1Natalya Yu. Vasilieva2Noureddine Issaoui3Yuriy N. Malyar4Aleksandr A. Kondrasenko5Valentina S. Borovkova6Angelina V. Miroshnikova7Anna S. Kazachenko8Omar Al-Dossary9Marek J. Wojcik10Yaroslava D. Berezhnaya11Evgeniy V. Elsuf’ev12Department of Organic and Analytical Chemistry, Institute of Nonferrous Metals and Materials Science, Siberian Federal University, pr. Svobodny 79, 660041 Krasnoyarsk, RussiaVocational School of Food, Agriculture and Livestock, University of Bingöl, Bingöl 12000, TurkeyDepartment of Organic and Analytical Chemistry, Institute of Nonferrous Metals and Materials Science, Siberian Federal University, pr. Svobodny 79, 660041 Krasnoyarsk, RussiaLaboratory of Quantum and Statistical Physics (LR18ES18), Faculty of Sciences, University of Monastir, Monastir 5079, TunisiaDepartment of Organic and Analytical Chemistry, Institute of Nonferrous Metals and Materials Science, Siberian Federal University, pr. Svobodny 79, 660041 Krasnoyarsk, RussiaInstitute of Chemistry and Chemical Technology, Krasnoyarsk Scientific Center, Siberian Branch, Russian Academy of Sciences, Akademgorodok, 50, bld. 24, 660036 Krasnoyarsk, RussiaDepartment of Organic and Analytical Chemistry, Institute of Nonferrous Metals and Materials Science, Siberian Federal University, pr. Svobodny 79, 660041 Krasnoyarsk, RussiaDepartment of Organic and Analytical Chemistry, Institute of Nonferrous Metals and Materials Science, Siberian Federal University, pr. Svobodny 79, 660041 Krasnoyarsk, RussiaDepartment of Organic and Analytical Chemistry, Institute of Nonferrous Metals and Materials Science, Siberian Federal University, pr. Svobodny 79, 660041 Krasnoyarsk, RussiaDepartment of Physics and Astronomy, College of Science, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi ArabiaFaculty of Chemistry, Jagiellonian University, 30-387 Krakow, PolandInstitute of Chemistry and Chemical Technology, Krasnoyarsk Scientific Center, Siberian Branch, Russian Academy of Sciences, Akademgorodok, 50, bld. 24, 660036 Krasnoyarsk, RussiaInstitute of Chemistry and Chemical Technology, Krasnoyarsk Scientific Center, Siberian Branch, Russian Academy of Sciences, Akademgorodok, 50, bld. 24, 660036 Krasnoyarsk, RussiaBetulin is an important triterpenoid substance isolated from birch bark, which, together with its sulfates, exhibits important bioactive properties. We report on a newly developed method of betulin sulfation with sulfamic acid in pyridine in the presence of an Amberlyst<sup>®</sup>15 solid acid catalyst. It has been shown that this catalyst remains stable when being repeatedly (up to four cycles) used and ensures obtaining of sulfated betulin with a sulfur content of ~10%. The introduction of the sulfate group into the betulin molecule has been proven by Fourier-transform infrared, ultraviolet-visible, and nuclear magnetic resonance spectroscopy. The Fourier-transform infrared (FTIR) spectra contain absorption bands at 1249 and 835–841 cm<sup>−1</sup>; in the UV spectra, the peak intensity decreases; and, in the nuclear magnetic resonance (NMR) spectra, of betulin disulfate, carbons С3 and С28 are completely shifted to the weak-field region (to 88.21 and 67.32 ppm, respectively) with respect to betulin. Using the potentiometric titration method, the product of acidity constants K<sub>1</sub> and K<sub>2</sub> of a solution of the betulin disulfate H<sup>+</sup> form has been found to be 3.86 × 10<sup>–6</sup> ± 0.004. It has been demonstrated by the thermal analysis that betulin and the betulin disulfate sodium salt are stable at temperatures of up to 240 and 220 °C, respectively. The density functional theory method has been used to obtain data on the most stable conformations, molecular electrostatic potential, frontier molecular orbitals, and mulliken atomic charges of betulin and betulin disulfate and to calculate the spectral characteristics of initial and sulfated betulin, which agree well with the experimental data.https://www.mdpi.com/1422-0067/23/3/1602betulinsulfationcatalysisdensity functional theory (DFT)sulfated betulin |
| spellingShingle | Aleksandr S. Kazachenko Feride Akman Natalya Yu. Vasilieva Noureddine Issaoui Yuriy N. Malyar Aleksandr A. Kondrasenko Valentina S. Borovkova Angelina V. Miroshnikova Anna S. Kazachenko Omar Al-Dossary Marek J. Wojcik Yaroslava D. Berezhnaya Evgeniy V. Elsuf’ev Catalytic Sulfation of Betulin with Sulfamic Acid: Experiment and DFT Calculation International Journal of Molecular Sciences betulin sulfation catalysis density functional theory (DFT) sulfated betulin |
| title | Catalytic Sulfation of Betulin with Sulfamic Acid: Experiment and DFT Calculation |
| title_full | Catalytic Sulfation of Betulin with Sulfamic Acid: Experiment and DFT Calculation |
| title_fullStr | Catalytic Sulfation of Betulin with Sulfamic Acid: Experiment and DFT Calculation |
| title_full_unstemmed | Catalytic Sulfation of Betulin with Sulfamic Acid: Experiment and DFT Calculation |
| title_short | Catalytic Sulfation of Betulin with Sulfamic Acid: Experiment and DFT Calculation |
| title_sort | catalytic sulfation of betulin with sulfamic acid experiment and dft calculation |
| topic | betulin sulfation catalysis density functional theory (DFT) sulfated betulin |
| url | https://www.mdpi.com/1422-0067/23/3/1602 |
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