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Issue 24, 2019
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Regioselective synthesis, isomerisation, in vitro oestrogenic activity, and copolymerisation of bisguaiacol F (BGF) isomers

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Abstract

Bisguaiacol F (BGF), a potentially safer and renewable bisphenol A (BPA) replacement made from lignin-derivable vanillyl alcohol (p-VA), is a promising building block for future aromatic biopolymers. Unfortunately, like BPA synthesis, this electrophilic condensation reaction is also prone to regioselectivity issues, giving rise to m,p′- and o,p′-BGF byproducts. In this work, the hitherto unconsidered influence of m,p′-BGF, viz. the main isomeric byproduct of p,p′-BGF synthesis, on the physicochemical properties of poly(BGF carbonate) (BGF-PC) was systematically investigated by random copolymerisation with different fractions of pure m,p′-BGF (25, 50 and 75 wt%). To do so, the elusive m,p′-isomer was made in unparalleled regioselectivity (72%) by alkylation condensation of isovanillyl alcohol (m-VA) with guaiacol. Surprisingly, no isomeric scrambling due to acid-catalysed isomerisation was encountered for pure BGF isomers, which strongly facilitates their synthesis in contrast to petrochemical bisphenol F (BPF). Furthermore, to ensure safer chemical design, an in vitro human oestrogen receptor α (hERα) transactivation assay was performed. Both pure m,p′- and p,p′-BGF displayed a significantly reduced oestrogenic potency (∼426–457 times lower affinity than BPA) and oestrogenic efficacy (∼39–50% of BPA's maximum induction). Interestingly, mutual comparison between p,p′-BPF and p,p′-BGF reveals and proves for the first time the direct link between ortho-methoxy substitution and reduced in vitro oestrogenic activity (for transactivation of hERα). In contrast to o,p′-BPA, viz. the main byproduct of p,p′-BPA synthesis, m,p′-BGF was proven suitable for utilization in thermoplastics, thereby avoiding time-consuming and labour-intensive (re)crystallizations to obtain regioisomerically pure p,p′-BGF.

Graphical abstract: Regioselective synthesis, isomerisation, in vitro oestrogenic activity, and copolymerisation of bisguaiacol F (BGF) isomers

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Supplementary files

Article information


Submitted
26 Jul 2019
Accepted
02 Oct 2019
First published
03 Oct 2019

Green Chem., 2019,21, 6622-6633
Article type
Paper

Regioselective synthesis, isomerisation, in vitro oestrogenic activity, and copolymerisation of bisguaiacol F (BGF) isomers

S. Koelewijn, D. Ruijten, L. Trullemans, T. Renders, P. Van Puyvelde, H. Witters and B. F. Sels, Green Chem., 2019, 21, 6622
DOI: 10.1039/C9GC02619C

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