Pyrolytic elimination of ethylene from ethoxyquinolines and ethoxyisoquinolines: a computational study
Abstract This work reports a thermo-kinetic study on unimolecular thermal decomposition of some ethoxyquinolines and ethoxyisoquinolines derivatives (1-ethoxyisoquinoline (1-EisoQ), 2-ethoxyquinoline (2-EQ), 3-ethoxyquinoline (3-EQ), 3-ethoxyisoquinoline (3-EisoQ), 4-ethoxyquinoline (4-EQ), 4-ethoxy...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2023-04-01
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| Series: | Scientific Reports |
| Online Access: | https://doi.org/10.1038/s41598-023-33272-2 |
| _version_ | 1797841047783473152 |
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| author | Mohamed A. Abdel-Rahman Mohamed F. Shibl Mohamed A. M. Mahmoud |
| author_facet | Mohamed A. Abdel-Rahman Mohamed F. Shibl Mohamed A. M. Mahmoud |
| author_sort | Mohamed A. Abdel-Rahman |
| collection | DOAJ |
| description | Abstract This work reports a thermo-kinetic study on unimolecular thermal decomposition of some ethoxyquinolines and ethoxyisoquinolines derivatives (1-ethoxyisoquinoline (1-EisoQ), 2-ethoxyquinoline (2-EQ), 3-ethoxyquinoline (3-EQ), 3-ethoxyisoquinoline (3-EisoQ), 4-ethoxyquinoline (4-EQ), 4-ethoxyisoquinoline (4-EisoQ), 5-ethoxyquinoline (5-EQ), 5-ethoxyisoquinoline (5-EisoQ), 8-ethoxyquinoline (8-EQ) and 8-ethoxyisoquinoline (8-EisoQ)) using density functional theory DFT (BMK, MPW1B95, M06-2X) and ab initio complete basis set-quadratic Becke3 (CBS-QB3) calculations. In the course of the decomposition of the investigated systems, ethylene is eliminated with the production of either keto or enol tautomer. The six-membered transition state structure encountered in the path of keto formation is much lower in energy than the four-membered transition state required to give enol form. Rate constants and activation energies for the decomposition of 1-EisoQ, 2-EQ, 3-EQ, 3-EisoQ, 4-EQ, 4-EisoQ, 5-EQ, 5-EisoQ, 8-EQ, and 8-EisoQ have been estimated at different temperatures and pressures using conventional transition state theory combined with Eckart tunneling and the unimolecular statistical Rice–Ramsperger–Kassel–Marcus theories. The tunneling correction is significant at temperatures up to 1000 K. Rate constants results reveal that ethylene elimination and keto production are favored kinetically and thermodynamically over the whole temperature range of 400–1200 K and the rates of the processes under study increase with the rising of pressure up to 1 atm. |
| first_indexed | 2024-04-09T16:24:38Z |
| format | Article |
| id | doaj.art-f4f74ff3747e435199ebbf7ce3cfd591 |
| institution | Directory Open Access Journal |
| issn | 2045-2322 |
| language | English |
| last_indexed | 2024-04-09T16:24:38Z |
| publishDate | 2023-04-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Scientific Reports |
| spelling | doaj.art-f4f74ff3747e435199ebbf7ce3cfd5912023-04-23T11:17:27ZengNature PortfolioScientific Reports2045-23222023-04-0113112010.1038/s41598-023-33272-2Pyrolytic elimination of ethylene from ethoxyquinolines and ethoxyisoquinolines: a computational studyMohamed A. Abdel-Rahman0Mohamed F. Shibl1Mohamed A. M. Mahmoud2Chemistry Department, Faculty of Science, Suez UniversityRenewable Energy Program, Center for Sustainable Development, College of Arts and Sciences, Qatar UniversityBasic Sciences Department, Tanta Higher Institute of Engineering and TechnologyAbstract This work reports a thermo-kinetic study on unimolecular thermal decomposition of some ethoxyquinolines and ethoxyisoquinolines derivatives (1-ethoxyisoquinoline (1-EisoQ), 2-ethoxyquinoline (2-EQ), 3-ethoxyquinoline (3-EQ), 3-ethoxyisoquinoline (3-EisoQ), 4-ethoxyquinoline (4-EQ), 4-ethoxyisoquinoline (4-EisoQ), 5-ethoxyquinoline (5-EQ), 5-ethoxyisoquinoline (5-EisoQ), 8-ethoxyquinoline (8-EQ) and 8-ethoxyisoquinoline (8-EisoQ)) using density functional theory DFT (BMK, MPW1B95, M06-2X) and ab initio complete basis set-quadratic Becke3 (CBS-QB3) calculations. In the course of the decomposition of the investigated systems, ethylene is eliminated with the production of either keto or enol tautomer. The six-membered transition state structure encountered in the path of keto formation is much lower in energy than the four-membered transition state required to give enol form. Rate constants and activation energies for the decomposition of 1-EisoQ, 2-EQ, 3-EQ, 3-EisoQ, 4-EQ, 4-EisoQ, 5-EQ, 5-EisoQ, 8-EQ, and 8-EisoQ have been estimated at different temperatures and pressures using conventional transition state theory combined with Eckart tunneling and the unimolecular statistical Rice–Ramsperger–Kassel–Marcus theories. The tunneling correction is significant at temperatures up to 1000 K. Rate constants results reveal that ethylene elimination and keto production are favored kinetically and thermodynamically over the whole temperature range of 400–1200 K and the rates of the processes under study increase with the rising of pressure up to 1 atm.https://doi.org/10.1038/s41598-023-33272-2 |
| spellingShingle | Mohamed A. Abdel-Rahman Mohamed F. Shibl Mohamed A. M. Mahmoud Pyrolytic elimination of ethylene from ethoxyquinolines and ethoxyisoquinolines: a computational study Scientific Reports |
| title | Pyrolytic elimination of ethylene from ethoxyquinolines and ethoxyisoquinolines: a computational study |
| title_full | Pyrolytic elimination of ethylene from ethoxyquinolines and ethoxyisoquinolines: a computational study |
| title_fullStr | Pyrolytic elimination of ethylene from ethoxyquinolines and ethoxyisoquinolines: a computational study |
| title_full_unstemmed | Pyrolytic elimination of ethylene from ethoxyquinolines and ethoxyisoquinolines: a computational study |
| title_short | Pyrolytic elimination of ethylene from ethoxyquinolines and ethoxyisoquinolines: a computational study |
| title_sort | pyrolytic elimination of ethylene from ethoxyquinolines and ethoxyisoquinolines a computational study |
| url | https://doi.org/10.1038/s41598-023-33272-2 |
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