Department of Chemistry, University of Durham, South Road, Durham DH1 3LE, UK.
Molecules. 2019 Nov 16;24(22):4154. doi: 10.3390/molecules24224154.
A simple protocol yielding -substituted nitrosophenols from phenols is demonstrated, in the form of copper(II) (nitrosophenolato) complexes. The developed methodology was applied to a range of substrates, confirming the role of the copper in both the formation and protection of the challenging 1, 2-substitution pattern. Using polymer supported thiourea, the Cu could be stripped from the complexes and thus enabled the isolation or identification of the uncoordinated ligands and their decomposition products, in yields generally low in line with the intrinsic high reactivity of 2-nitrosophenols. The product complexes are useful intermediates as demonstrated in revisiting a formal [4 + 2] cycloaddition with dimethylacetylene dicarboxylate to synthesise bicyclic products in variable yields, revealing the product has a novel structure different from those previously reported in the literature.
本文展示了一种简单的从酚类化合物生成 - 取代亚硝基苯酚的方法，即通过铜(II)（亚硝基苯氧络合物）配合物的形式。所开发的方法学已应用于一系列底物，证实了铜在形成和保护具有挑战性的 1,2-取代模式中的作用。使用聚合物负载的硫脲，可以从配合物中除去铜，从而能够分离或鉴定未配位的配体及其分解产物，其产率通常与 2-亚硝基苯酚的固有高反应性一致。所得到的产物配合物是有用的中间体，如在重新进行与二甲基乙炔二羧酸的形式 [4 + 2] 环加成反应以可变产率合成双环产物中所证明的，揭示了产物具有与文献中先前报道的不同的新颖结构。
