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以5-溴-2-甲氧基-1,3-苯二甲醛与二乙烯三胺通过[2+2]缩合,合成了一个新的六氮杂二十四元大环配体,并在[Cu(CH_3CN)]_4ClO_4存在下生成Cu(Ⅰ)大环配合物,然后在空气(或氧气)中氧化,得到了新的大环双核Cu(Ⅱ)配合物,用多种方法对其进行了表征,用~1HNMR谱等方法鉴定了氧化产物.实验结果证明:在Cu(Ⅰ)配合物氧化过程中,能使配体环上的一个甲氧基发生断裂,形成苯氧桥和水桥联的Cu(Ⅱ)配合物.在木质素酶等单加氧酶的氧化过程中也伴随着氧化去甲基作用.本文首次用大环配合物对这一过程进行了模拟,并测定了氧化反应中的吸氧量和吸氧速率常数.
A novel hexaazate twenty-four membered macrocyclic ligand was synthesized by condensation of 5-bromo-2-methoxy-1,3-benzenedicarboxyaldehyde with diethylenetriamine through [2 + 2] Cu (Ⅰ) macrocyclic complexes are formed in the presence of [Cu (CH 3 CN)] 4ClO 4 and then oxidized in the air (or oxygen) to give new macrocyclic binuclear Cu (Ⅱ) complexes which are subjected to various methods The results showed that during the oxidation of Cu (Ⅰ) complex, a methoxy group in the ring of the ligand could be broken to form phenoxyl bridge and water bridge Linked Cu (Ⅱ) complex, and oxidative demethylation is also involved in the oxidation of monooxygenase, such as ligninase. In this paper, the macrocyclic complexes were used for the first time to simulate this process and the oxidation Oxygen uptake and oxygen uptake rate constant during the reaction.