Mechanism of Air Oxidation of the Fragrance Terpene Geraniol

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• 作者：Carina B&auml ; cktorp ; Lina Hagvall ; Anna Bö ; rje ; Ann-Therese Karlberg ; Per-Ola Norrby ; Gunnar Nyman
• 刊名：Journal of Chemical Theory and Computation
• 出版年：2008
• 出版时间：January 2008
• 年：2008
• 卷：4
• 期：1
• 页码：101 - 106
• 全文大小：117K
• 年卷期：v.4,no.1(January 2008)
• ISSN：1549-9626

文摘

The fragrance terpene geraniol autoxidizes upon air exposure and forms a mixtureof oxidation products, some of which are skin sensitizers. Reactions of geraniol with OB>2 havebeen studied with DFT (B3LYP) and the computational results compared to experimentallyobserved product ratios. The oxidation is initiated by hydrogen abstraction, forming an allylicradical which combines with an O₂ molecule to yield an intermediate peroxyl radical. In thesubsequent step, geraniol differs from previously studied cases, in which the radical chain reactionis propagated through intermolecular hydrogen abstraction. The hydroxy-substituted allylic peroxylradical prefers an intramolecular rearrangement, producing observable aldehydes and thehydroperoxyl radical, which in turn can propagate the radical reaction. Secondary oxidationproducts like epoxides and formates were also considered, and plausible reaction pathways forformation are proposed.