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Vol. 31 No. 3 (2019): Vol 31 Issue 3

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Theoretical Study of Sigmatropic Rearrangement of Cycloprop-2-en-1-ol and its Fluorine Derivatives: Pericyclic or Pseudopericyclic Character from NICS and LLPE

https://doi.org/10.14233/ajchem.2019.21646
A. Sangeetha
Department of Chemistry, Government Thirumagal Mills College, Gudiyattam-632602, India
A. Thaminum Ansari
PG & Research Department of Chemistry, Muthurangam Government Arts College (Autonomous), Vellore-632002, India
Jebakumar Jeevan
Department of Chemistry, Rajeswari Vedachalam Government Arts College, Chengalpet-603001, India
S. Jayaprakash
Department of Chemistry, Islamiah College, Vaniyambadi-635752, India

Corresponding Author(s) : A. Sangeetha

a.sangeetha1502@gmail.com

Asian Journal of Chemistry, Vol. 31 No. 3 (2019): Vol 31 Issue 3

Abstract

Sigmatropic rearrangement reaction of cycloprop-2-en-1-ol and its fluorine derivatives has been studied theoretically in gas phase and its energy barrier has been calculated. Nucleus-independent chemical shift (NICS) shows sigmatropic rearrangement of cycloprop-2-en-1-ol is pericyclic in nature whereas fluorine derivatives show pseudopericyclic and pericyclic nature. Substitution of fluorine atom at ring is found to increase the energy barrier for –OH migration, while substitution at oxygen atom reduces the barrier. To know the involvement of lone pair of electrons during the reaction, lone pair electron present on oxygen atom is locked by hydrogen bonding. CR-CCSD(T)/6-311+G** levels are used to study the reactions more accurately.

Keywords

Pseudopericyclic reaction Aromaticity DFT calculations ab initio calculations Sigmatropic rearrangement reaction
Sangeetha, A., Ansari, A. T., Jeevan, J., & Jayaprakash, S. (2019). Theoretical Study of Sigmatropic Rearrangement of Cycloprop-2-en-1-ol and its Fluorine Derivatives: Pericyclic or Pseudopericyclic Character from NICS and LLPE. Asian Journal of Chemistry, 31(3), 597–601. https://doi.org/10.14233/ajchem.2019.21646
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