Theoretical Study on Elementary Reaction Steps in Thermal Decomposition Processes of Syringol-Type Monolignol Compounds

Yuki Furutani, Yuki Dohara, Shinji Kudo, Jun Ichiro Hayashi, Koyo Norinaga

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

This paper theoretically investigated a large number of reaction pathways and kinetics to describe the vapor-phase pyrolytic behavior of several syringol-type monolignol compounds that are derived from the primary pyrolysis of lignin: 1-(4-hydroxy-3,5-dimethoxyphenyl)prop-2-en-1-one (HDPP), sinapyl alcohol, 3-hydroxy-1-(4-hydroxy-3,5-dimethoxyphenyl)propan-1-one (HHDPP), 1-(4-hydroxy-3,5-dimethoxyphenyl)propane-1,3-diol (HDPPD), and syringol. The possible pyrolytic pathways involving unimolecular decomposition, addition, and abstraction reactions were investigated by comparing the energy barriers calculated at the B3LYP/6-311++G(d,p) level. In the proposed pathways, all syringol-type monolignols containing a side chain undergo its cleavage to form syringol through the formation of syringaldehyde or 4-vinylsyringol. Syringol is then converted into two products: (a) pyrogallol via the homolysis of the O-CH3 bond and hydrogenation or (b) guaiacol via addition of an H atom with a carbon bearing methoxyl group in syrignol and the subsequent demethoxylation. The pyrolytic pathways of pyrogallol are classified into two processes: (a) the concerted dehydrogenation of the two hydroxyl H atoms and the unimolecular decomposition to produce acetylene (C2H2), ethynol (C2HOH), and CO or (b) the displacement of an OH with H to produce catechol and resorcinol. Additionally, HDPP undergoes O-CH3 bond cleavage to form but-1-en-3-yne. The high-pressure limit rate constants for all the proposed elementary reaction steps were evaluated on the basis of transition state theory.

Original languageEnglish
Pages (from-to)822-831
Number of pages10
JournalJournal of Physical Chemistry A
Volume122
Issue number3
DOIs
Publication statusPublished - Jan 25 2018

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

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