期刊
JOURNAL OF PHYSICAL CHEMISTRY A
卷 116, 期 50, 页码 12242-12248出版社
AMER CHEMICAL SOC
DOI: 10.1021/jp3104694
关键词
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资金
- Division of Chemical Sciences, Geosciences, Office of Basic Energy Sciences, U.S. Department of Energy
- National Center for Computational Sciences at Oak Ridge National Laboratory [DE-AC05-00OR22725]
- Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy
We investigate phenyl shift and subsequent beta-scission reactions for PhCHXCH center dot OPh [X = H, OH], which are part of the pyrolysis mechanism of phenethyl phenyl ether (PPE) and alpha-hydroxy PPE. PPE and its derivatives are model compounds for the most common linkage in lignin, the beta-O-4 linkage. We use density functional theory to locate transition states and equilibrium structures and kinetic Monte Carlo in combination with transition-state theory for kinetic simulations. Oxygen-carbon and carbon-carbon phenyl shift reactions proceed through cyclic intermediates with similar barriers. However, while subsequent beta-scission of the oxygen-carbon shift products proceeds with virtually no barrier, the activation energy for beta-scission of the carbon-carbon shift products exceeds 15 kcal/mol. We found that about 15% of beta-radical conversion can be attributed to carbon-carbon shift for PPE and alpha-hydroxy PPE at 618 K. Whereas the oxygen-carbon shift reaction has been established as an integral part of the pyrolysis mechanism of PPE and its derivatives, participation of the carbon-carbon shift reaction has not been shown previously.
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