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Regioselective synthesis, isomerisation, in vitro oestrogenic activity, and copolymerisation of bisguaiacol F (BGF) isomers†
Green Chemistry ( IF 9.3 ) Pub Date : 2019-10-03 , DOI: 10.1039/c9gc02619c Steven-Friso Koelewijn 1, 2, 3, 4, 5 , Dieter Ruijten 1, 2, 3, 4, 5 , Laura Trullemans 1, 2, 3, 4, 5 , Tom Renders 1, 2, 3, 4, 5 , Peter Van Puyvelde 3, 4, 6, 7, 8 , Hilda Witters 5, 9, 10, 11, 12 , Bert F. Sels 1, 2, 3, 4, 5
Green Chemistry ( IF 9.3 ) Pub Date : 2019-10-03 , DOI: 10.1039/c9gc02619c Steven-Friso Koelewijn 1, 2, 3, 4, 5 , Dieter Ruijten 1, 2, 3, 4, 5 , Laura Trullemans 1, 2, 3, 4, 5 , Tom Renders 1, 2, 3, 4, 5 , Peter Van Puyvelde 3, 4, 6, 7, 8 , Hilda Witters 5, 9, 10, 11, 12 , Bert F. Sels 1, 2, 3, 4, 5
Affiliation
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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.
中文翻译：
bisguaiacol F（BGF）异构体的 区域选择性合成，异构化，体外雌激素活性和共聚†
Bisguaiacol F（BGF）是一种潜在安全，可再生的双酚A（BPA）替代品，由木质素衍生的香草醇（p -VA）制成，是未来芳香族生物聚合物的有前途的基石。不幸的是，与BPA合成一样，该亲电缩合反应也容易发生区域选择性问题，产生m，p'-和o，p' -BGF副产物。在这项工作中，迄今未被考虑的影响米，p '-BGF，即。主要异构体副产物p，p通过与不同比例的纯m，p' -BGF（25、50和75 wt％）的无规共聚，系统地研究了聚-BGF碳酸酯（BGF-PC）的理化性质上的′-BGF合成。为此，通过异香草醛醇（m -VA）与愈创木酚的烷基化缩合反应，制得了难以捉摸的m，p'-异构体（72％）。出乎意料的是，对于纯BGF异构体，没有遇到由于酸催化的异构化引起的异构加扰，这与石化双酚F（BPF）相比，极大地促进了它们的合成。此外，为了确保更安全的化学设计，在体外进行了人类雌激素受体α（hERα）反式激活试验。纯的m，p′-和p，p′ -BGF都显示出显着降低的雌激素效能（亲和力比BPA低约426-457倍）和雌激素功效（约为BPA最大诱导量的39-50％）。有趣的是，p，p′ -BPF和p，p′ -BGF之间的相互比较揭示并首次证明了邻甲氧基取代与降低的体外雌激素活性（用于hERα的反式激活）之间的直接联系。与o相比，p' -BPA，即。已证明p，p′ -BPA合成的主要副产物m，p′ -BGF适用于热塑性塑料，从而避免了费时费力的劳动（重）结晶，从而获得了区域异构纯p，p′ -BGF。
更新日期：2020-01-02
中文翻译：
bisguaiacol F（BGF）异构体的 区域选择性合成，异构化，体外雌激素活性和共聚†
Bisguaiacol F（BGF）是一种潜在安全，可再生的双酚A（BPA）替代品，由木质素衍生的香草醇（p -VA）制成，是未来芳香族生物聚合物的有前途的基石。不幸的是，与BPA合成一样，该亲电缩合反应也容易发生区域选择性问题，产生m，p'-和o，p' -BGF副产物。在这项工作中，迄今未被考虑的影响米，p '-BGF，即。主要异构体副产物p，p通过与不同比例的纯m，p' -BGF（25、50和75 wt％）的无规共聚，系统地研究了聚-BGF碳酸酯（BGF-PC）的理化性质上的′-BGF合成。为此，通过异香草醛醇（m -VA）与愈创木酚的烷基化缩合反应，制得了难以捉摸的m，p'-异构体（72％）。出乎意料的是，对于纯BGF异构体，没有遇到由于酸催化的异构化引起的异构加扰，这与石化双酚F（BPF）相比，极大地促进了它们的合成。此外，为了确保更安全的化学设计，在体外进行了人类雌激素受体α（hERα）反式激活试验。纯的m，p′-和p，p′ -BGF都显示出显着降低的雌激素效能（亲和力比BPA低约426-457倍）和雌激素功效（约为BPA最大诱导量的39-50％）。有趣的是，p，p′ -BPF和p，p′ -BGF之间的相互比较揭示并首次证明了邻甲氧基取代与降低的体外雌激素活性（用于hERα的反式激活）之间的直接联系。与o相比，p' -BPA，即。已证明p，p′ -BPA合成的主要副产物m，p′ -BGF适用于热塑性塑料，从而避免了费时费力的劳动（重）结晶，从而获得了区域异构纯p，p′ -BGF。
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