Products of Photo- and Thermochemical Rearrangement of 19-Membered di-<i>tert</i>-Butyl-Azoxybenzocrown
The preparation and characterization of products of the photochemical and thermochemical rearrangements of 19-membered azoxybenzocrowns with two, bulky, <i>tert</i>-butyl substituents in benzene rings in the <i>para</i> positions to oligooxyethylene fragments (<i>meta&l...
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| Format: | Article |
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MDPI AG
2022-03-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/27/6/1835 |
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| author | Ewa Wagner-Wysiecka Paulina Szulc Elżbieta Luboch Jarosław Chojnacki Paweł Sowiński Katarzyna Szwarc-Karabyka |
| author_facet | Ewa Wagner-Wysiecka Paulina Szulc Elżbieta Luboch Jarosław Chojnacki Paweł Sowiński Katarzyna Szwarc-Karabyka |
| author_sort | Ewa Wagner-Wysiecka |
| collection | DOAJ |
| description | The preparation and characterization of products of the photochemical and thermochemical rearrangements of 19-membered azoxybenzocrowns with two, bulky, <i>tert</i>-butyl substituents in benzene rings in the <i>para</i> positions to oligooxyethylene fragments (<i>meta</i> positions to azoxy group, i.e., <b><i>t</i>-Bu-19-Azo-O</b> have been presented. In photochemical rearrangement, two colored typical products were expected, i.e., 19-membered <i>o</i>-hydroxy-<i>m,m</i>′-di-<i>tert</i>-butyl-azobenzocrown (<b><i>t</i>-Bu</b>-<b>19-<i>o</i>-OH</b>) and 19-membered <i>p</i>-hydroxy-<i>m,m</i>′-di-<i>tert</i>-butyl-azobenzocrown (<b><i>t</i>-Bu</b>-<b>19-<i>p</i>-OH</b>). In experiments, two colored atypical macrocyclic derivatives, one 6-membered and one 5-membered ring, bearing an aldehyde group (<b><i>t</i>-Bu-19-al</b>) or intramolecular ester group (<b><i>t</i>-Bu-20-ester</b>), were obtained. Photochemical rearrangement led to one more macrocyclic product being isolated and identified: a 17-membered colorless compound, without an azo moiety, <b><i>t</i>-Bu-17-<i>p</i>-OH</b>. The yield of the individual compounds was significantly influenced by the reaction conditions. Thermochemical rearrangement led to <b><i>t</i>-Bu-20-ester</b> as the main product. The structures of the four crystalline products of the rearrangement—<b><i>t</i>-Bu</b>-<b>19-<i>o</i>-OH</b>, <b><i>t</i>-Bu</b>-<b>19-<i>p</i>-OH</b>, <b><i>t</i>-Bu-20-ester</b> and <b><i>t</i>-Bu-17-<i>p</i>-OH</b>—were determined by the X-ray method. Structures in solution of atypical derivatives (<b><i>t</i>-Bu-19-al</b> and <b><i>t</i>-Bu-20-ester</b>) and <b><i>t</i>-Bu</b>-<b>19-<i>p</i>-OH</b> 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. <sup>1</sup>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 <b><i>t</i>-Bu</b>-<b>19-<i>o</i>-OH</b>. |
| first_indexed | 2024-03-09T13:10:17Z |
| format | Article |
| id | doaj.art-18ceae6d54434e828ea627f368f42094 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T13:10:17Z |
| publishDate | 2022-03-01 |
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| record_format | Article |
| series | Molecules |
| spelling | doaj.art-18ceae6d54434e828ea627f368f420942023-11-30T21:41:56ZengMDPI AGMolecules1420-30492022-03-01276183510.3390/molecules27061835Products of Photo- and Thermochemical Rearrangement of 19-Membered di-<i>tert</i>-Butyl-AzoxybenzocrownEwa Wagner-Wysiecka0Paulina Szulc1Elżbieta Luboch2Jarosław Chojnacki3Paweł Sowiński4Katarzyna Szwarc-Karabyka5Department of Chemistry and Technology of Functional Materials, Faculty of Chemistry, Gdańsk University of Technology, Narutowicza Street 11/12, 80-233 Gdańsk, PolandDepartment of Chemistry and Technology of Functional Materials, Faculty of Chemistry, Gdańsk University of Technology, Narutowicza Street 11/12, 80-233 Gdańsk, PolandDepartment of Chemistry and Technology of Functional Materials, Faculty of Chemistry, Gdańsk University of Technology, Narutowicza Street 11/12, 80-233 Gdańsk, PolandDepartment of Inorganic Chemistry, Faculty of Chemistry, Gdańsk University of Technology, Narutowicza Street 11/12, 80-233 Gdańsk, PolandNuclear Magnetic Resonance Laboratory, Faculty of Chemistry, Gdańsk University of Technology, Narutowicza Street 11/12, 80-233 Gdańsk, PolandNuclear Magnetic Resonance Laboratory, Faculty of Chemistry, Gdańsk University of Technology, Narutowicza Street 11/12, 80-233 Gdańsk, PolandThe preparation and characterization of products of the photochemical and thermochemical rearrangements of 19-membered azoxybenzocrowns with two, bulky, <i>tert</i>-butyl substituents in benzene rings in the <i>para</i> positions to oligooxyethylene fragments (<i>meta</i> positions to azoxy group, i.e., <b><i>t</i>-Bu-19-Azo-O</b> have been presented. In photochemical rearrangement, two colored typical products were expected, i.e., 19-membered <i>o</i>-hydroxy-<i>m,m</i>′-di-<i>tert</i>-butyl-azobenzocrown (<b><i>t</i>-Bu</b>-<b>19-<i>o</i>-OH</b>) and 19-membered <i>p</i>-hydroxy-<i>m,m</i>′-di-<i>tert</i>-butyl-azobenzocrown (<b><i>t</i>-Bu</b>-<b>19-<i>p</i>-OH</b>). In experiments, two colored atypical macrocyclic derivatives, one 6-membered and one 5-membered ring, bearing an aldehyde group (<b><i>t</i>-Bu-19-al</b>) or intramolecular ester group (<b><i>t</i>-Bu-20-ester</b>), were obtained. Photochemical rearrangement led to one more macrocyclic product being isolated and identified: a 17-membered colorless compound, without an azo moiety, <b><i>t</i>-Bu-17-<i>p</i>-OH</b>. The yield of the individual compounds was significantly influenced by the reaction conditions. Thermochemical rearrangement led to <b><i>t</i>-Bu-20-ester</b> as the main product. The structures of the four crystalline products of the rearrangement—<b><i>t</i>-Bu</b>-<b>19-<i>o</i>-OH</b>, <b><i>t</i>-Bu</b>-<b>19-<i>p</i>-OH</b>, <b><i>t</i>-Bu-20-ester</b> and <b><i>t</i>-Bu-17-<i>p</i>-OH</b>—were determined by the X-ray method. Structures in solution of atypical derivatives (<b><i>t</i>-Bu-19-al</b> and <b><i>t</i>-Bu-20-ester</b>) and <b><i>t</i>-Bu</b>-<b>19-<i>p</i>-OH</b> 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. <sup>1</sup>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 <b><i>t</i>-Bu</b>-<b>19-<i>o</i>-OH</b>.https://www.mdpi.com/1420-3049/27/6/1835macrocycleazo compoundphotochemistryrearrangementtautomerismspectroscopy |
| spellingShingle | Ewa Wagner-Wysiecka Paulina Szulc Elżbieta Luboch Jarosław Chojnacki Paweł Sowiński Katarzyna Szwarc-Karabyka Products of Photo- and Thermochemical Rearrangement of 19-Membered di-<i>tert</i>-Butyl-Azoxybenzocrown Molecules macrocycle azo compound photochemistry rearrangement tautomerism spectroscopy |
| title | Products of Photo- and Thermochemical Rearrangement of 19-Membered di-<i>tert</i>-Butyl-Azoxybenzocrown |
| title_full | Products of Photo- and Thermochemical Rearrangement of 19-Membered di-<i>tert</i>-Butyl-Azoxybenzocrown |
| title_fullStr | Products of Photo- and Thermochemical Rearrangement of 19-Membered di-<i>tert</i>-Butyl-Azoxybenzocrown |
| title_full_unstemmed | Products of Photo- and Thermochemical Rearrangement of 19-Membered di-<i>tert</i>-Butyl-Azoxybenzocrown |
| title_short | Products of Photo- and Thermochemical Rearrangement of 19-Membered di-<i>tert</i>-Butyl-Azoxybenzocrown |
| title_sort | products of photo and thermochemical rearrangement of 19 membered di i tert i butyl azoxybenzocrown |
| topic | macrocycle azo compound photochemistry rearrangement tautomerism spectroscopy |
| url | https://www.mdpi.com/1420-3049/27/6/1835 |
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