OH-Initiated Reactions of p-Coumaryl Alcohol Relevant to the Lignin Pyrolysis. Part I. Potential Energy Surface Analysis

Document Type

Article

Publication Date

4-4-2019

Abstract

Cinnamyl alcohols such as p-coumaryl alcohol (p-CMA) are lignin models and precursors (monolignols) and the most important primary products of lignin pyrolysis. However, the detection of monomers is not straightforward since they either undergo secondary transformations or repolymerize to contribute to the char formation. Both concerted-molecular and free-radical pathways are involved in these processes. Our recent fundamentally based theoretical and low-temperature matrix-isolation-EPR studies of cinnamyl alcohols highlighted the role of side-chain reactivity in diversity of pyrolysis products and provided a network of the chemically activated H + p-CMA reactions (Asatryan et al. J. Phys. Chem. A, 2017, 121, 3352-3371). The readily available hydroxyl radicals also can trigger a cascade of free-radical processes. Here, we present a comprehensive potential energy surface (PES) analysis of the OH + p-CMA reaction using various DFT and ab initio protocols. Since the p-CMA involves both an alkyl OH-group and a side-chain double bond, the title reaction can also serve as a relevant model for reactions of unsaturated alcohols with hydroxyl radicals to form various oxygenates including polyhydric alcohols which are abundant in nature. The newly identified pathways suggest certain alternatives to the known radical reactions. Of particular interest are the roaming-like low-energy dehydration reactions to generate a variety of O- and C-centered intermediate radicals, which are primarily transformed into the phenolic compounds observed in pyrolysis experiments. Several concerted unimolecular decomposition pathways for p-CMA are also revealed, not considered previously, such as the migration of terminal OH-group, and/or its splitting over the ipso-C and ortho-C atoms of the benzene ring to form bicyclic oxispiro- and chromene compounds represented in natural lignin.

Identifier

85063399145 (Scopus)

Publication Title

Journal of Physical Chemistry A

External Full Text Location

https://doi.org/10.1021/acs.jpca.9b00185

e-ISSN

15205215

ISSN

10895639

PubMed ID

30848901

First Page

2570

Last Page

2585

Issue

13

Volume

123

Grant

1330311

Fund Ref

University at Buffalo

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