Department of Chemistry and Technology of Functional Materials, Faculty of Chemistry, Gdańsk University of Technology, Narutowicza Street 11/12, 80-233 Gdańsk, Poland.
Department of Inorganic Chemistry, Faculty of Chemistry, Gdańsk University of Technology, Narutowicza Street 11/12, 80-233 Gdańsk, Poland.
Molecules. 2022 Mar 11;27(6):1835. doi: 10.3390/molecules27061835.
The preparation and characterization of products of the photochemical and thermochemical rearrangements of 19-membered azoxybenzocrowns with two, bulky, -butyl substituents in benzene rings in the positions to oligooxyethylene fragments ( positions to azoxy group, i.e., have been presented. In photochemical rearrangement, two colored typical products were expected, i.e., 19-membered -hydroxy-'-di--butyl-azobenzocrown (-) and 19-membered -hydroxy-'-di--butyl-azobenzocrown (-). In experiments, two colored atypical macrocyclic derivatives, one 6-membered and one 5-membered ring, bearing an aldehyde group () or intramolecular ester group (), were obtained. Photochemical rearrangement led to one more macrocyclic product being isolated and identified: a 17-membered colorless compound, without an azo moiety, . The yield of the individual compounds was significantly influenced by the reaction conditions. Thermochemical rearrangement led to as the main product. The structures of the four crystalline products of the rearrangement--, -, and -were determined by the X-ray method. Structures in solution of atypical derivatives ( and ) and - were defined using NMR spectroscopy. For the newly obtained hydroxyazobenzocrowns, the azo-phenol⇄quinone-hydrazone tautomeric equilibrium was investigated using spectroscopic methods. Complexation studies of alkali and alkaline earth metal cations were studied using UV-Vis absorption spectroscopy. H NMR spectroscopy was additionally used to study the cation recognition of metal cations. Cation binding studies in acetonitrile have shown high selectivity towards calcium over magnesium for -.
已经介绍了在苯环的 位带有两个体积庞大的叔丁基取代基的 19 元偶氮苯并冠醚与聚氧亚乙基片段（即靠近偶氮基团的位置）的光化学和热化学重排产物的制备和特性。在光化学重排中，预计会得到两种有色典型产物，即 19 元 -羟基-'-二-叔丁基-偶氮苯并冠醚（-）和 19 元 -羟基-'-二-叔丁基-偶氮苯并冠醚（-）。在实验中，得到了两种有色非典型大环衍生物，一种带有醛基（）或分子内酯基（）的 6 元和 5 元环。光化学重排导致分离并鉴定出另一种大环产物：无色化合物，没有偶氮部分，。各化合物的产率受反应条件的显著影响。热化学重排导致主要产物为。通过 X 射线法确定了重排的四个结晶产物--、-、-和-的结构。使用 NMR 光谱法确定了非典型衍生物（和）和-的溶液结构。对于新获得的羟基偶氮苯并冠醚，使用光谱方法研究了偶氮酚⇄醌腙互变异构平衡。使用紫外可见吸收光谱研究了碱金属和碱土金属阳离子的络合研究。此外，还使用 1H NMR 光谱法研究了金属阳离子对阳离子的识别。在乙腈中的阳离子结合研究表明，-对钙具有高选择性，而对镁则没有。
