Cleavage of lignin model compounds and ligninox using aqueous oxalic acid

Ashley C. Lindsay, Shinji Kudo, Jonathan Sperry

Research output: Contribution to journalArticle

Abstract

Aqueous oxalic acid cleaves oxidised β-O-4 lignin model compounds by two distinct mechanisms that are dependent on the presence of the hydroxymethyl substituent. Various β-O-4 phenoxyacetophenones that do not contain the hydroxymethyl substituent undergo oxidative cleavage upon exposure to aqueous oxalic acid in the presence of air, likely through concerted ring opening of a dioxetane intermediate to give the corresponding benzoic acid and phenyl formate. Importantly, detrimental side reactions arising from singlet oxygen and hydroperoxy radicals (from both O2 and oxalic acid) are minimal when the cleavage is run under air compared to neat oxygen. When oxidised β-O-4 lignin model compounds bearing the hydroxymethyl group are cleaved by aqueous oxalic acid, the resulting diketone and phenol products arise from a redox neutral cleavage that is analogous to the formic acid-sodium formate mediated lignin cleavage process reported by Stahl. Aqueous oxalic acid also cleaves lignin itself, with oxidised milled wood lignin (MWLox) from Pinus radiata giving a 14% yield of ethyl acetate soluble aromatics with good selectivity for vanillin. Aqueous oxalic acid appears to be a promising lignin cleavage system given the benign, bio-based reagents, absence of metals and organic solvents and a simple extraction procedure that enables oxalic acid recycling.

Original languageEnglish
Pages (from-to)7408-7415
Number of pages8
JournalOrganic and Biomolecular Chemistry
Volume17
Issue number31
DOIs
Publication statusPublished - Jan 1 2019

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Oxalic Acid
lignin
oxalic acid
Lignin
formic acid
cleavage
formates
Bearings (structural)
Air
Pinus
Singlet Oxygen
Benzoic Acid
air
benzoic acid
Recycling
oxygen
recycling
Phenol
phenols
Organic solvents

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry

Cite this

Cleavage of lignin model compounds and ligninox using aqueous oxalic acid. / Lindsay, Ashley C.; Kudo, Shinji; Sperry, Jonathan.

In: Organic and Biomolecular Chemistry, Vol. 17, No. 31, 01.01.2019, p. 7408-7415.

Research output: Contribution to journalArticle

Lindsay, Ashley C. ; Kudo, Shinji ; Sperry, Jonathan. / Cleavage of lignin model compounds and ligninox using aqueous oxalic acid. In: Organic and Biomolecular Chemistry. 2019 ; Vol. 17, No. 31. pp. 7408-7415.
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