Original scientific paper

https://doi.org/10.5562/cca4249

Reactivity and Intramolecular Interactions in Linalool: A Computational Study Using Reactivity Descriptors, NCI, NBO, and QTAIM Analyses

Karen Canseco-Sandoval ; Área Académica de Química, Universidad Autónoma del Estado de Hidalgo, carretera Pachuca–Tulancingo, 42184, Mineral de la Reforma, Hidalgo. México
Clara Hilda Rios-Reyes ; Área Académica de Química, Universidad Autónoma del Estado de Hidalgo, carretera Pachuca–Tulancingo, 42184, Mineral de la Reforma, Hidalgo. México
Luis Humberto Mendoza-Huizar orcid.org/0000-0003-2373-4624 ; Área Académica de Química, Universidad Autónoma del Estado de Hidalgo, carretera Pachuca–Tulancingo, 42184, Mineral de la Reforma, Hidalgo. México *

* Corresponding author.

Supplements: cca4249_supplement.pdf

Abstract

In this study, the chemical reactivity of linalool was examined using global and local reactivity descriptors calculated at the X/6-311++G(2d,2p) level of theory (X = B3LYP, M06, M06L, ωB97XD, and MP2). The global reactivity indices indicate that linalool exhibits moderate electrophilic character. Fukui functions and frontier molecular orbital analysis identify C6 and C7 carbon atoms as the most reactive sites toward electrophilic and radical species, while nucleophiles preferentially interact with the hydrogen atom of the hydroxyl group and the hydrogen atoms attached to C5 and C6. Molecular electrostatic potential maps indicate that the hydroxyl group and the C6–C7 region are the most polarized regions of the molecule. Noncovalent interaction analysis suggests a weak intramolecular H–O···H–C interactions. However, Natural Bond Orbital (NBO) and Quantum Theory of Atoms in Molecules analyses show that this feature corresponds to a weak noncovalent contact rather than a conventional hydrogen bond. Also, NBO analysis indicates that the conformational stability of linalool is largely controlled by intramolecular hyperconjugative σ→σ* interactions along the carbon framework, enhanced by lone-pair donation from the hydroxyl oxygen.

Keywords

linalool; enantiomers; reactivity; fukui; MP2

Hrčak ID:

349698

URI

https://hrcak.srce.hr/349698

Publication date:

21.5.2026.

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