Experimental and Theoretical Study on the Homodimerization Mechanism of 3-Acetylcoumarin
In the present study, the reaction conditions for homodimerization process of 3-acetylcoumarin were achieved under sonication using combination of zinc and metallic salt (ZnCl<sub>2</sub> or Zn(OAc)<sub>2</sub>). Appropriate frequency and sound amplitude have been identified...
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| Format: | Article |
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MDPI AG
2022-10-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/27/21/7228 |
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| author | Kristina B. Simeonova Ana I. Koleva Anna-Mariya R. Zlatanova Nevena I. Petkova-Yankova Hristiyan A. Aleksandrov Petko St. Petkov Rositca D. Nikolova |
| author_facet | Kristina B. Simeonova Ana I. Koleva Anna-Mariya R. Zlatanova Nevena I. Petkova-Yankova Hristiyan A. Aleksandrov Petko St. Petkov Rositca D. Nikolova |
| author_sort | Kristina B. Simeonova |
| collection | DOAJ |
| description | In the present study, the reaction conditions for homodimerization process of 3-acetylcoumarin were achieved under sonication using combination of zinc and metallic salt (ZnCl<sub>2</sub> or Zn(OAc)<sub>2</sub>). Appropriate frequency and sound amplitude have been identified as significant variables for the initiation of the reaction. On the base of first principal calculations and experimental results, the mechanism of the reaction was investigated. The relative stability of the possible intermediates has been compared, including evaluation on the ionic and radical reaction pathways for the dimerization process. Theoretical results suggested that the radical mechanism is more favorable. The C-C bond formation between the calculated radical intermediates occurs spontaneously (∆G = −214 kJ/mol for ZnCl<sub>2</sub>, −163 kJ/mol in the case of Zn(OAc)<sub>2</sub>), which proves the possibility for the homodimerization of 3-acetylcoumarin via formation of radical species. Both experimental and theoretical data clarified the activation role of the solvent on the reactivity of the Zn-salt. The formation of complexes of solvent molecules with Zn-atom from the ZnCl<sub>2</sub> reduces the energy barrier for the dissociation of Zn-Cl bond and facilitate the formation of the dimeric product. |
| first_indexed | 2024-03-09T18:49:30Z |
| format | Article |
| id | doaj.art-f729f201815a43349c2db9d195fa28bb |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T18:49:30Z |
| publishDate | 2022-10-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-f729f201815a43349c2db9d195fa28bb2023-11-24T06:00:53ZengMDPI AGMolecules1420-30492022-10-012721722810.3390/molecules27217228Experimental and Theoretical Study on the Homodimerization Mechanism of 3-AcetylcoumarinKristina B. Simeonova0Ana I. Koleva1Anna-Mariya R. Zlatanova2Nevena I. Petkova-Yankova3Hristiyan A. Aleksandrov4Petko St. Petkov5Rositca D. Nikolova6Faculty of Chemistry and Pharmacy, Sofia University “St. Kliment Ohridski”, 1 James Bourchier Blvd, 1164 Sofia, BulgariaFaculty of Chemistry and Pharmacy, Sofia University “St. Kliment Ohridski”, 1 James Bourchier Blvd, 1164 Sofia, BulgariaFaculty of Chemistry and Pharmacy, Sofia University “St. Kliment Ohridski”, 1 James Bourchier Blvd, 1164 Sofia, BulgariaFaculty of Chemistry and Pharmacy, Sofia University “St. Kliment Ohridski”, 1 James Bourchier Blvd, 1164 Sofia, BulgariaFaculty of Chemistry and Pharmacy, Sofia University “St. Kliment Ohridski”, 1 James Bourchier Blvd, 1164 Sofia, BulgariaFaculty of Chemistry and Pharmacy, Sofia University “St. Kliment Ohridski”, 1 James Bourchier Blvd, 1164 Sofia, BulgariaFaculty of Chemistry and Pharmacy, Sofia University “St. Kliment Ohridski”, 1 James Bourchier Blvd, 1164 Sofia, BulgariaIn the present study, the reaction conditions for homodimerization process of 3-acetylcoumarin were achieved under sonication using combination of zinc and metallic salt (ZnCl<sub>2</sub> or Zn(OAc)<sub>2</sub>). Appropriate frequency and sound amplitude have been identified as significant variables for the initiation of the reaction. On the base of first principal calculations and experimental results, the mechanism of the reaction was investigated. The relative stability of the possible intermediates has been compared, including evaluation on the ionic and radical reaction pathways for the dimerization process. Theoretical results suggested that the radical mechanism is more favorable. The C-C bond formation between the calculated radical intermediates occurs spontaneously (∆G = −214 kJ/mol for ZnCl<sub>2</sub>, −163 kJ/mol in the case of Zn(OAc)<sub>2</sub>), which proves the possibility for the homodimerization of 3-acetylcoumarin via formation of radical species. Both experimental and theoretical data clarified the activation role of the solvent on the reactivity of the Zn-salt. The formation of complexes of solvent molecules with Zn-atom from the ZnCl<sub>2</sub> reduces the energy barrier for the dissociation of Zn-Cl bond and facilitate the formation of the dimeric product.https://www.mdpi.com/1420-3049/27/21/7228reaction mechanismhomodimerization3-acetylcoumarindensity functional theory calculationscoumarinDFT modeling |
| spellingShingle | Kristina B. Simeonova Ana I. Koleva Anna-Mariya R. Zlatanova Nevena I. Petkova-Yankova Hristiyan A. Aleksandrov Petko St. Petkov Rositca D. Nikolova Experimental and Theoretical Study on the Homodimerization Mechanism of 3-Acetylcoumarin Molecules reaction mechanism homodimerization 3-acetylcoumarin density functional theory calculations coumarin DFT modeling |
| title | Experimental and Theoretical Study on the Homodimerization Mechanism of 3-Acetylcoumarin |
| title_full | Experimental and Theoretical Study on the Homodimerization Mechanism of 3-Acetylcoumarin |
| title_fullStr | Experimental and Theoretical Study on the Homodimerization Mechanism of 3-Acetylcoumarin |
| title_full_unstemmed | Experimental and Theoretical Study on the Homodimerization Mechanism of 3-Acetylcoumarin |
| title_short | Experimental and Theoretical Study on the Homodimerization Mechanism of 3-Acetylcoumarin |
| title_sort | experimental and theoretical study on the homodimerization mechanism of 3 acetylcoumarin |
| topic | reaction mechanism homodimerization 3-acetylcoumarin density functional theory calculations coumarin DFT modeling |
| url | https://www.mdpi.com/1420-3049/27/21/7228 |
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