期刊
JOURNAL OF ORGANIC CHEMISTRY
卷 76, 期 7, 页码 2195-2203出版社
AMER CHEMICAL SOC
DOI: 10.1021/jo2000385
关键词
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资金
- Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences, U.S. Department of Energy [DE-AC05-00OR22725]
- National Science Foundation
The phenyl-shift reaction for the beta-radical of phenethyl phenyl ether (PhCH2CHOPh, beta-PPE) is an integral step in the pyrolysis of PPE, which is a model compound for the beta-O-4 linkage in lignin. We investigated the influence of natural occurring substituents (hydroxy, methoxy) on the reaction rate by calculating relative rate constants using density functional theory in combination with transition state theory, including anharmonic correction for low-frequency modes. The phenyl-shift reaction proceeds through an oxaspiro[2.5]octadienyl radical intermediate and the overall rate constants were computed invoking the steady-state approximation (its validity was confirmed). Substituents on the phenethyl ring have only little influence on the rate constants. If a methoxy substituent is located in the para position of the phenyl ring adjacent to the ether oxygen, the energies of the intermediate and second transition state are lowered, but the overall rate constant is not significantly altered. This is a consequence of the dominating first transition from reactant to intermediate in the overall rate constant. In contrast, o- and di-o-methoxy substituents significantly accelerate the phenyl-migration rate compared to beta-PPE.
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