Patel Anjan, Rosenau Thomas
Department of Natural Sciences and Sustainable Resources, Institute of Chemistry of Renewable Resources, BOKU University, Konrad-Lorenz-Straße 24, 3430 Tulln, Austria.
Molecules. 2025 Aug 4;30(15):3257. doi: 10.3390/molecules30153257.
Tocopheramines are a class of antioxidants which are distinguished from tocopherols (vitamin E) by the presence of an amino group instead of the phenolic hydroxyl group. α-Tocopheramine is intensively studied for biomedical applications but also as a stabilizer for synthetic and natural polymers, in particular for cellulose solutions and spinning dopes for cellulosic fibers. This study addresses a fundamental difference in the oxidation chemistry of α-tocopheramine and its tocopherol counterpart: while the formation of the ortho-quinone methide (o-QM) involving C-5a is one of the most fundamental reactions of α-tocopherol, the corresponding ortho-iminoquinone methide (o-IQM) derived from α-tocopheramine has been elusive so far. Synthesis of the transient intermediate succeeded initially via 5a-hydroxy-α-tocopheramine, and its occurrence was confirmed by dimerization to the corresponding spiro-dimer and by trapping with ethyl vinyl ether. Eventually, suitable oxidation conditions were found which allowed for the generation of the o-IQM directly from α-tocopheramine. The underlying oxidation chemistry of α-tocopherol and α-tocopheramine is concisely discussed.
生育胺是一类抗氧化剂，它与生育酚（维生素E）的区别在于存在一个氨基而非酚羟基。α-生育胺在生物医学应用方面受到广泛研究，同时也用作合成聚合物和天然聚合物的稳定剂，特别是用于纤维素溶液以及纤维素纤维的纺丝原液。本研究探讨了α-生育胺与其生育酚对应物在氧化化学方面的一个根本差异：虽然涉及C-5a的邻醌甲基化物（o-QM）的形成是α-生育酚最基本的反应之一，但迄今为止，源自α-生育胺的相应邻亚氨基醌甲基化物（o-IQM）一直难以捉摸。瞬态中间体的合成最初通过5a-羟基-α-生育胺成功实现，并且通过二聚形成相应的螺二聚体以及用乙基乙烯基醚捕获来证实其存在。最终，找到了合适的氧化条件，使得可以直接从α-生育胺生成o-IQM。本文简要讨论了α-生育酚和α-生育胺的潜在氧化化学。
