木质素酸催化解聚反应中间体原位转化的芳香族单体,Journal of the American Chemical Society

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木质素酸催化解聚反应中间体原位转化的芳香族单体
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2015-06-05 , DOI: 10.1021/jacs.5b03693
Peter J. Deuss ₁ , Martin Scott ₁ , Fanny Tran ₂ , Nicholas J. Westwood ₂ , Johannes G. de Vries _{1,

3} , Katalin Barta ₁

Affiliation

将木质素转化为定义明确的芳香族化学品是一个极具吸引力的目标，但通常会受到所形成碎片的再缩合的阻碍，尤其是在酸解过程中。在这里，我们描述了新策略，这些策略显着抑制了这种不受欢迎的途径，从而产生了以前没有系统地从木质素中靶向的多种芳香族化合物。模型研究表明，催化量的三氟甲磺酸在裂解木质素中含量最高的 β-O-4 键方面非常有效。醛产物被确定为裂解条件下副反应的主要原因。通过与二醇反应并通过原位催化氢化或脱羰来捕获这种不稳定的化合物，可以得到三组不同的芳香族化合物，高收率缩醛、乙醇和乙基芳香族化合物以及甲基芳香族化合物。尤其，当这些方法成功扩展到木质素时，获得了相同的产品组。此外，显着抑制了较高分子量副产物的形成，表明醛中间体在这些过程中发挥了重要作用。所描述的策略有可能普遍适用于从木质素生产有趣的芳香族化合物。

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Aromatic Monomers by in Situ Conversion of Reactive Intermediates in the Acid-Catalyzed Depolymerization of Lignin

Conversion of lignin into well-defined aromatic chemicals is a highly attractive goal but is often hampered by recondensation of the formed fragments, especially in acidolysis. Here, we describe new strategies that markedly suppress such undesired pathways to result in diverse aromatic compounds previously not systematically targeted from lignin. Model studies established that a catalytic amount of triflic acid is very effective in cleaving the β-O-4 linkage, most abundant in lignin. An aldehyde product was identified as the main cause of side reactions under cleavage conditions. Capturing this unstable compound by reaction with diols and by in situ catalytic hydrogenation or decarbonylation lead to three distinct groups of aromatic compounds in high yields acetals, ethanol and ethyl aromatics, and methyl aromatics. Notably, the same product groups were obtained when these approaches were successfully extended to lignin. In addition, the formation of higher molecular weight side products was markedly suppressed, indicating that the aldehyde intermediates play a significant role in these processes. The described strategy has the potential to be generally applicable for the production of interesting aromatic compounds from lignin.

更新日期：2015-06-05

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