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Pyrolysis studies have been conducted at 375 °C on several silica-immobilized phenethyl phenyl ether (PPE) model compounds, representative of related β-O-4 aryl ether linkages in lignin, to explore the impact of restricted mass transport on reaction pathways. As found previously for fluid-phase PPE, two competitive free-radical decay pathways are operative including a significant rearrangement pathway involving an O,C-phenyl shift for surface-attached PhCH2CH•OPh radicals. The selectivity for the rearrangement pathway is found to be sensitive to substituents and, in particular, to the structure of neighboring spacer molecules on the surface. In contrast to solution-phase behavior, dilution of PPE molecules on the surface with rigid aromatic spacers such as biphenyl or naphthalene hinder the rearrangement path. This phenomenon, attributed to steric constraints that decrease the rate of the 1,2-phenyl shift, is not observed when a more flexible spacer molecule (diphenylmethane) is employed. An improved knowledge of the pathways involved is important since this rearrangement pathway, which was also observed in the pyrolysis of α-aryl ether models, can result in the formation of valuable chemicals (aryl aldehydes and ketones) or undesirable refractory compounds (biphenyls and diphenylmethanes) during the thermochemical processing of lignin.

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