Reaction of either 2-pyrone or 1,4-oxazinone with acetylene follows the sequence of cycloaddition - cycloreversion through concerted mechanism. Transition states for both cycloaddition and cycloreversion pathways have been obtained in both the cases by modelling the reactions at B3LYP/6-31g (d) level. Cycloreversion is faster than cycloaddition in the case of 2-pyrone due to the enhancement of aromaticity resulting the product as benzene. In contrast, oxazinone has rapid cycloaddition. It is ascribed to the presence of nitrogen in this system. Removal of either CO2 or HCN is plausible in this mechanism to complete the reaction. Even though two pathways are feasible for cycloreversion, CO2 extrusion is more preferable than HCN elimination. In these two studied molecules, there is an enhancement of aromaticity up to transition states like any other pericyclic reaction and further it diminishes during cycloaddition. Further, aromaticity is specifically augmented in cycloreversion phase during CO2 elimination resulting to yield pyridine whereas competitive HCN elimination results in the formation of 2-pyrone which is less facile. In both the molecules the aromatic enhancement of the cycloreversion is substantiated through the study of magnetic susceptibility of the ring fragment along the reaction coordinate. Further the study also reveals the effect of halogen substituted at different carbons of 2-pyrone ring.
| Published in | International Journal of Pharmacy and Chemistry (Volume 7, Issue 1) |
| DOI | 10.11648/j.ijpc.20210701.13 |
| Page(s) | 13-21 |
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Aromaticity, Cycloaddition-cycloreversion Reactin, DFT Study, Intrinsic Reaction Coordinate
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APA Style
Padmanaban Kalpana, Lakshminarayanan Akilandeswari, Ponnambalam Venuvanalingam. (2021). Tandem Cycloaddition-Cycloreversion of 2-pyrone and 1,4-oxazinone with Acetylene - A DFT Insight. International Journal of Pharmacy and Chemistry, 7(1), 13-21. https://doi.org/10.11648/j.ijpc.20210701.13
ACS Style
Padmanaban Kalpana; Lakshminarayanan Akilandeswari; Ponnambalam Venuvanalingam. Tandem Cycloaddition-Cycloreversion of 2-pyrone and 1,4-oxazinone with Acetylene - A DFT Insight. Int. J. Pharm. Chem. 2021, 7(1), 13-21. doi: 10.11648/j.ijpc.20210701.13
AMA Style
Padmanaban Kalpana, Lakshminarayanan Akilandeswari, Ponnambalam Venuvanalingam. Tandem Cycloaddition-Cycloreversion of 2-pyrone and 1,4-oxazinone with Acetylene - A DFT Insight. Int J Pharm Chem. 2021;7(1):13-21. doi: 10.11648/j.ijpc.20210701.13
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Download@article{10.11648/j.ijpc.20210701.13,
author = {Padmanaban Kalpana and Lakshminarayanan Akilandeswari and Ponnambalam Venuvanalingam},
title = {Tandem Cycloaddition-Cycloreversion of 2-pyrone and 1,4-oxazinone with Acetylene - A DFT Insight},
journal = {International Journal of Pharmacy and Chemistry},
volume = {7},
number = {1},
pages = {13-21},
doi = {10.11648/j.ijpc.20210701.13},
url = {https://doi.org/10.11648/j.ijpc.20210701.13},
eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ijpc.20210701.13},
abstract = {Reaction of either 2-pyrone or 1,4-oxazinone with acetylene follows the sequence of cycloaddition - cycloreversion through concerted mechanism. Transition states for both cycloaddition and cycloreversion pathways have been obtained in both the cases by modelling the reactions at B3LYP/6-31g (d) level. Cycloreversion is faster than cycloaddition in the case of 2-pyrone due to the enhancement of aromaticity resulting the product as benzene. In contrast, oxazinone has rapid cycloaddition. It is ascribed to the presence of nitrogen in this system. Removal of either CO2 or HCN is plausible in this mechanism to complete the reaction. Even though two pathways are feasible for cycloreversion, CO2 extrusion is more preferable than HCN elimination. In these two studied molecules, there is an enhancement of aromaticity up to transition states like any other pericyclic reaction and further it diminishes during cycloaddition. Further, aromaticity is specifically augmented in cycloreversion phase during CO2 elimination resulting to yield pyridine whereas competitive HCN elimination results in the formation of 2-pyrone which is less facile. In both the molecules the aromatic enhancement of the cycloreversion is substantiated through the study of magnetic susceptibility of the ring fragment along the reaction coordinate. Further the study also reveals the effect of halogen substituted at different carbons of 2-pyrone ring.},
year = {2021}
}
TY - JOUR T1 - Tandem Cycloaddition-Cycloreversion of 2-pyrone and 1,4-oxazinone with Acetylene - A DFT Insight AU - Padmanaban Kalpana AU - Lakshminarayanan Akilandeswari AU - Ponnambalam Venuvanalingam Y1 - 2021/02/27 PY - 2021 N1 - https://doi.org/10.11648/j.ijpc.20210701.13 DO - 10.11648/j.ijpc.20210701.13 T2 - International Journal of Pharmacy and Chemistry JF - International Journal of Pharmacy and Chemistry JO - International Journal of Pharmacy and Chemistry SP - 13 EP - 21 PB - Science Publishing Group SN - 2575-5749 UR - https://doi.org/10.11648/j.ijpc.20210701.13 AB - Reaction of either 2-pyrone or 1,4-oxazinone with acetylene follows the sequence of cycloaddition - cycloreversion through concerted mechanism. Transition states for both cycloaddition and cycloreversion pathways have been obtained in both the cases by modelling the reactions at B3LYP/6-31g (d) level. Cycloreversion is faster than cycloaddition in the case of 2-pyrone due to the enhancement of aromaticity resulting the product as benzene. In contrast, oxazinone has rapid cycloaddition. It is ascribed to the presence of nitrogen in this system. Removal of either CO2 or HCN is plausible in this mechanism to complete the reaction. Even though two pathways are feasible for cycloreversion, CO2 extrusion is more preferable than HCN elimination. In these two studied molecules, there is an enhancement of aromaticity up to transition states like any other pericyclic reaction and further it diminishes during cycloaddition. Further, aromaticity is specifically augmented in cycloreversion phase during CO2 elimination resulting to yield pyridine whereas competitive HCN elimination results in the formation of 2-pyrone which is less facile. In both the molecules the aromatic enhancement of the cycloreversion is substantiated through the study of magnetic susceptibility of the ring fragment along the reaction coordinate. Further the study also reveals the effect of halogen substituted at different carbons of 2-pyrone ring. VL - 7 IS - 1 ER -
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