Theoretical investigation of linalool oxidation.
Artikel i vetenskaplig tidskrift, 2006

This study concerns the autoxidation of one of the most used fragrances in daily life, linalool (3,7-dimethyl-1,6-octadien-3-ol). It reacts with O2 to form hydroperoxides, which are known to be important contact allergens. Pathways for hydroperoxide formation are investigated by means of quantum mechanical electronic structure calculations. Optimized molecular geometries and harmonic vibrational frequencies are determined using density functional theory (DFT). Insight into how the addition of O2 to linalool occurs is obtained by establishing a theoretical framework and systematically investigating three smaller systems: propene, 2-methyl-2-butene, and 2-methyl-2-pentene. 2-Methyl-2-pentene was chosen as a model system and used to compare with linalool. This theoretical study characterizes the linalool-O2 biradical intermediate state, which constitutes a branching point for the further oxidation reactions pathways. Thus, the observed linalool oxidation product spectrum is discussed in terms of a direct reaction path, the ene-type mechanism, and the radical mechanism. The major hydroperoxide found in experiments is 7-hydroperoxy-3,7-dimethyl-octa-1,5-diene-3-ol, and the calculated results support this finding.

Chemical

Free Radicals

chemistry

chemistry

Monoterpenes

Alkenes

Computer Simulation

chemistry

chemistry

Models

chemistry

Insecticides

Fatty Alcohols

Molecular Structure

Quantum Theory

Oxidation-Reduction

Författare

Carina Bäcktorp

Göteborgs universitet

J R Tobias Johnsson Wass

Göteborgs universitet

Itai Panas

Chalmers, Kemi- och bioteknik, Oorganisk miljökemi

Maria Sköld

Göteborgs universitet

Anna Börje

Göteborgs universitet

Gunnar Nyman

Göteborgs universitet

Journal of Physical Chemistry A

1089-5639 (ISSN) 1520-5215 (eISSN)

Vol. 110 12204-12

Ämneskategorier

Fysikalisk kemi

DOI

10.1021/jp0603278

PubMed

17078616