Direct Amination of Nitroquinoline Derivatives via Nucleophilic Displacement of Aromatic Hydrogen
The vicarious nucleophilic substitution of hydrogen (VNS) reaction in electron-deficient nitroquinolines was studied. Properties of all new products have been characterized by several techniques: MS, HRMS, FTIR, GC-MS, electronic absorption spectroscopy, and multinuclear NMR. The structures of 4-chl...
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| Format: | Article |
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MDPI AG
2021-03-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/26/7/1857 |
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| author | Jakub Wantulok Daniel Swoboda Jacek E. Nycz Maria Książek Joachim Kusz Jan Grzegorz Małecki Vladimír Kubíček |
| author_facet | Jakub Wantulok Daniel Swoboda Jacek E. Nycz Maria Książek Joachim Kusz Jan Grzegorz Małecki Vladimír Kubíček |
| author_sort | Jakub Wantulok |
| collection | DOAJ |
| description | The vicarious nucleophilic substitution of hydrogen (VNS) reaction in electron-deficient nitroquinolines was studied. Properties of all new products have been characterized by several techniques: MS, HRMS, FTIR, GC-MS, electronic absorption spectroscopy, and multinuclear NMR. The structures of 4-chloro-8-nitroquinoline, 8-(<i>tert</i>-butyl)-2-methyl-5-nitroquinoline, 9-(8-nitroquinolin-7-yl)-9<i>H</i>-carbazole and (<i>Z</i>)-7-(9<i>H</i>-carbazol-9-yl)-8-(hydroxyimino)quinolin-5(8<i>H</i>)-one were determined by single-crystal X-ray diffraction measurements. The 9-(8-nitroquinolin-7-yl)-9<i>H</i>-carbazole and (<i>Z</i>)-7-(9<i>H</i>-carbazol-9-yl)-8-(hydroxyimino)quinolin-5(8<i>H</i>)-one illustrate the nitro/nitroso conversion within VNS reaction. Additionally, 9-(8-isopropyl-2-((8-isopropyl-2-methyl-5-nitroquinolin-6-yl)methyl)-5-nitrosoquinolin-6-yl)-9<i>H</i>-carbazole is presented as a double VNS product. It is postulated that the potassium counterion interacts with the oxygen on the nitro group, which could influence nucleophile attack in that way. |
| first_indexed | 2024-03-10T12:54:11Z |
| format | Article |
| id | doaj.art-64aa08c3e22c4a69b690e16d59787026 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T12:54:11Z |
| publishDate | 2021-03-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-64aa08c3e22c4a69b690e16d597870262023-11-21T12:01:19ZengMDPI AGMolecules1420-30492021-03-01267185710.3390/molecules26071857Direct Amination of Nitroquinoline Derivatives via Nucleophilic Displacement of Aromatic HydrogenJakub Wantulok0Daniel Swoboda1Jacek E. Nycz2Maria Książek3Joachim Kusz4Jan Grzegorz Małecki5Vladimír Kubíček6Faculty of Science and Technology, Institute of Chemistry, University of Silesia in Katowice, ul. Szkolna 9, PL-40007 Katowice, PolandFaculty of Science and Technology, Institute of Chemistry, University of Silesia in Katowice, ul. Szkolna 9, PL-40007 Katowice, PolandFaculty of Science and Technology, Institute of Chemistry, University of Silesia in Katowice, ul. Szkolna 9, PL-40007 Katowice, PolandFaculty of Science and Technology, Institute of Physics, Univeristy of Silesia in Katowice, 75 Pułku Piechoty 1a, 41-500 Chorzów, PolandFaculty of Science and Technology, Institute of Physics, Univeristy of Silesia in Katowice, 75 Pułku Piechoty 1a, 41-500 Chorzów, PolandFaculty of Science and Technology, Institute of Chemistry, University of Silesia in Katowice, ul. Szkolna 9, PL-40007 Katowice, PolandFaculty of Pharmacy in Hradec Králové, Charles University Prague, Akademika Heyrovského 1203, 500 05 Hradec Králové, Czech RepublicThe vicarious nucleophilic substitution of hydrogen (VNS) reaction in electron-deficient nitroquinolines was studied. Properties of all new products have been characterized by several techniques: MS, HRMS, FTIR, GC-MS, electronic absorption spectroscopy, and multinuclear NMR. The structures of 4-chloro-8-nitroquinoline, 8-(<i>tert</i>-butyl)-2-methyl-5-nitroquinoline, 9-(8-nitroquinolin-7-yl)-9<i>H</i>-carbazole and (<i>Z</i>)-7-(9<i>H</i>-carbazol-9-yl)-8-(hydroxyimino)quinolin-5(8<i>H</i>)-one were determined by single-crystal X-ray diffraction measurements. The 9-(8-nitroquinolin-7-yl)-9<i>H</i>-carbazole and (<i>Z</i>)-7-(9<i>H</i>-carbazol-9-yl)-8-(hydroxyimino)quinolin-5(8<i>H</i>)-one illustrate the nitro/nitroso conversion within VNS reaction. Additionally, 9-(8-isopropyl-2-((8-isopropyl-2-methyl-5-nitroquinolin-6-yl)methyl)-5-nitrosoquinolin-6-yl)-9<i>H</i>-carbazole is presented as a double VNS product. It is postulated that the potassium counterion interacts with the oxygen on the nitro group, which could influence nucleophile attack in that way.https://www.mdpi.com/1420-3049/26/7/1857aminationvicarious nucleophilic substitution of hydrogennucleophilic aromatic substitution (S<sub>N</sub>Ar)nitrationheterocyclicSkraup |
| spellingShingle | Jakub Wantulok Daniel Swoboda Jacek E. Nycz Maria Książek Joachim Kusz Jan Grzegorz Małecki Vladimír Kubíček Direct Amination of Nitroquinoline Derivatives via Nucleophilic Displacement of Aromatic Hydrogen Molecules amination vicarious nucleophilic substitution of hydrogen nucleophilic aromatic substitution (S<sub>N</sub>Ar) nitration heterocyclic Skraup |
| title | Direct Amination of Nitroquinoline Derivatives via Nucleophilic Displacement of Aromatic Hydrogen |
| title_full | Direct Amination of Nitroquinoline Derivatives via Nucleophilic Displacement of Aromatic Hydrogen |
| title_fullStr | Direct Amination of Nitroquinoline Derivatives via Nucleophilic Displacement of Aromatic Hydrogen |
| title_full_unstemmed | Direct Amination of Nitroquinoline Derivatives via Nucleophilic Displacement of Aromatic Hydrogen |
| title_short | Direct Amination of Nitroquinoline Derivatives via Nucleophilic Displacement of Aromatic Hydrogen |
| title_sort | direct amination of nitroquinoline derivatives via nucleophilic displacement of aromatic hydrogen |
| topic | amination vicarious nucleophilic substitution of hydrogen nucleophilic aromatic substitution (S<sub>N</sub>Ar) nitration heterocyclic Skraup |
| url | https://www.mdpi.com/1420-3049/26/7/1857 |
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