Synthesis and complex formation with alkali metal cations of bis(benzocrown-ethers) with fragments of glycoluril

R&D registration number in UkrISTEI: 0119U002035

What priority area of ​​science and technology does it correspond to: fundamental scientific research on the most important problems of developing scientific, technical, socio-economic, socio-political, human potential to ensure Ukraine’s competitiveness in the world and sustainable development of society and the state.

Research: fundamental.

Source of funding: funds from the state budget.

Prospect for further implementation in 2021-2022: continued as fundamental.

Research level: no analogues in Ukraine.

Patent: no.

What additional actions require further research: additional funding, modern scientific equipment.

Brief description, advantages, further prospects for application.

By boiling for 2-3 weeks with a Dean-Stark nozzle to remove water from crown-containing benzyls with urea in benzene or toluene in the presence of trifluoroacetic acid as a catalyst with a yield of ≥ 70%, the obtained bis(benzocrown-ethers) with fragments. Methylation of the obtained compounds with methyl iodide in DMF in the presence of sodium hydride introduced methyl groups at the atoms of the glycoluril fragment of Nitrogen. The structure of bis (crown ether) with benzo-12-crown-4 fragments was confirmed by X-ray diffraction analysis. In the crystalline state, the classical U-shaped form of the molecule is observed. The complex formation of the obtained compounds with alkali metal cations was studied by spectrophotometric titration. It has been shown that the resulting crown-containing glycolurils form only 1:1 complexes with alkali metal cations. Compounds with 15-membered crown ether rings form the most stable sandwich-type complexes with rubidium and potassium cations and exhibit high potassium/sodium selectivity (3.5 orders of magnitude). The stability constants of complexes with potassium and rubidium ions are 1.5–2 orders of magnitude higher than those obtained for the cesium ion. Therefore, these compounds can be considered as promising chemosensors that allow the determination of potassium ions in the presence of large excesses of sodium ions, which is important for biological media. The results obtained significantly expand knowledge about the structure and properties of macroheterocyclic compounds and, in their significance, correspond to the world level.

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