Issue 7, 2023

Highly efficient synthesis of sustainable bisphenols from hydroxycinnamic acids

Abstract

Three stilbene based bisphenols: (E)-4,4′-(ethene-1,2-diyl)diphenol (1), (E)-4,4′-(ethene-1,2-diyl)bis(2-methoxyphenol) (2), and (E)-4,4′-(ethene-1,2-diyl)bis(2,6-dimethoxyphenol) (3) were synthesized from p-coumaric, ferulic, and sinapic acid, respectively. This was accomplished with a high-yielding two-step approach, which combined catalyst-free thermal decarboxylation of the cinnamic acids followed by olefin metathesis. The thermal decarboxylation proceeded in quantitative yield merely by refluxing the cinnamic acids in DMF under a nitrogen atmosphere. The resulting vinyl phenols were briefly isolated and then immediately subjected to olefin metathesis with a Grubbs–Hoveyda 2nd generation catalyst, which resulted in direct precipitation of the bisphenols from the reaction mixture. Overall yields of 1, 2, and 3 were 92, 88, and 85%, respectively, starting from the cinnamic acids. The compounds were isolated as pure solids without the need for crystallization or column chromatography. Bisphenol 1 was isomerized to the cis-isomer by irradiation with UV light. The resulting 80 : 20 cis : trans mixture exhibited a glass transition at low temperatures and a decreased melting temperature. To further expand the suite of bisphenols that can be produced from cinnamic acids, p-coumaric acid was directly converted into a 4-vinylphenol dimer by thermal decarboxylation/dimerization in a biphasic aqueous base/toluene solution to yield (E)-4,4′-(but-1-ene-1,3-diyl)diphenol (4). The ability to efficiently produce bisphenols from abundant, low-cost, and easily sourced bio-based substrates holds great promise for the development of more sustainable polymers.

Graphical abstract: Highly efficient synthesis of sustainable bisphenols from hydroxycinnamic acids

Supplementary files

Article information

Article type
Paper
Submitted
05 iyn 2023
Accepted
09 avq 2023
First published
11 avq 2023
This article is Open Access
Creative Commons BY-NC license

RSC Sustain., 2023,1, 1765-1772

Highly efficient synthesis of sustainable bisphenols from hydroxycinnamic acids

C. E. Zavala, N. A. Vest, J. E. Baca, D. D. Zhang, K. R. McClain and B. G. Harvey, RSC Sustain., 2023, 1, 1765 DOI: 10.1039/D3SU00175J

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