A simple route to 7-substituted Quinolin-2(1H)-ones from Meta-substituted anilines
Meta-substituted anilines are condensed with methyl 3,3-dimethoxypropionate in a two-step acylation, cyclization sequence to preferentially form 7-substituted quinolinones in an isomeric mixture with 5-substituted quinolinones. The product ratios in this previously unexplored class of substrates dep...
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| Language: | English |
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Elsevier
2025-03-01
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| Series: | Results in Chemistry |
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| Online Access: | http://www.sciencedirect.com/science/article/pii/S2211715625000724 |
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| author | Marisol Varela Ausec Mary K. Payne Jason R. Stewart Olivia M. Galando Eliott J. Wright Sara E.S. Martin |
| author_facet | Marisol Varela Ausec Mary K. Payne Jason R. Stewart Olivia M. Galando Eliott J. Wright Sara E.S. Martin |
| author_sort | Marisol Varela Ausec |
| collection | DOAJ |
| description | Meta-substituted anilines are condensed with methyl 3,3-dimethoxypropionate in a two-step acylation, cyclization sequence to preferentially form 7-substituted quinolinones in an isomeric mixture with 5-substituted quinolinones. The product ratios in this previously unexplored class of substrates depend on the steric and electronic properties of the aniline substituent. Within a series of halogenated anilines, selectivity varies directly with electronegativity and inversely with C–X bond length, up to 93:7 (R = F). For alkyl substituted anilines, a Charton analysis reveals a linear free-energy relationship between steric bulk of the alkyl substituent and selectivity for 7-substituted products, where selectivity for 7-substituted products increases with steric bulk of the alkyl substituent. Alkyl substituted quinolinones are generated with up to 97:3 selectivity for the 7-substituted product when R = tBu. |
| format | Article |
| id | doaj-art-f9f09098355f4e79abae3b9782ed885c |
| institution | Kabale University |
| issn | 2211-7156 |
| language | English |
| publishDate | 2025-03-01 |
| publisher | Elsevier |
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| series | Results in Chemistry |
| spelling | doaj-art-f9f09098355f4e79abae3b9782ed885c2025-02-09T05:00:06ZengElsevierResults in Chemistry2211-71562025-03-0114102089A simple route to 7-substituted Quinolin-2(1H)-ones from Meta-substituted anilinesMarisol Varela Ausec0Mary K. Payne1Jason R. Stewart2Olivia M. Galando3Eliott J. Wright4Sara E.S. Martin5Department of Chemistry, The College of Wooster, 931 College Mall, Wooster, OH 44691, USAProgram in Biochemistry and Molecular Biology, The College of Wooster, 931 College Mall, Wooster, OH 44691, USADepartment of Chemistry, The College of Wooster, 931 College Mall, Wooster, OH 44691, USAProgram in Biochemistry and Molecular Biology, The College of Wooster, 931 College Mall, Wooster, OH 44691, USADepartment of Chemistry, The College of Wooster, 931 College Mall, Wooster, OH 44691, USADepartment of Chemistry, The College of Wooster, 931 College Mall, Wooster, OH 44691, USA; Program in Biochemistry and Molecular Biology, The College of Wooster, 931 College Mall, Wooster, OH 44691, USA; Corresponding author at: Department of Chemistry, The College of Wooster, 931 College Mall, Wooster, OH, 44691, USA.Meta-substituted anilines are condensed with methyl 3,3-dimethoxypropionate in a two-step acylation, cyclization sequence to preferentially form 7-substituted quinolinones in an isomeric mixture with 5-substituted quinolinones. The product ratios in this previously unexplored class of substrates depend on the steric and electronic properties of the aniline substituent. Within a series of halogenated anilines, selectivity varies directly with electronegativity and inversely with C–X bond length, up to 93:7 (R = F). For alkyl substituted anilines, a Charton analysis reveals a linear free-energy relationship between steric bulk of the alkyl substituent and selectivity for 7-substituted products, where selectivity for 7-substituted products increases with steric bulk of the alkyl substituent. Alkyl substituted quinolinones are generated with up to 97:3 selectivity for the 7-substituted product when R = tBu.http://www.sciencedirect.com/science/article/pii/S2211715625000724HeterocycleQuinolinoneElectrophilic aromatic substitution |
| spellingShingle | Marisol Varela Ausec Mary K. Payne Jason R. Stewart Olivia M. Galando Eliott J. Wright Sara E.S. Martin A simple route to 7-substituted Quinolin-2(1H)-ones from Meta-substituted anilines Results in Chemistry Heterocycle Quinolinone Electrophilic aromatic substitution |
| title | A simple route to 7-substituted Quinolin-2(1H)-ones from Meta-substituted anilines |
| title_full | A simple route to 7-substituted Quinolin-2(1H)-ones from Meta-substituted anilines |
| title_fullStr | A simple route to 7-substituted Quinolin-2(1H)-ones from Meta-substituted anilines |
| title_full_unstemmed | A simple route to 7-substituted Quinolin-2(1H)-ones from Meta-substituted anilines |
| title_short | A simple route to 7-substituted Quinolin-2(1H)-ones from Meta-substituted anilines |
| title_sort | simple route to 7 substituted quinolin 2 1h ones from meta substituted anilines |
| topic | Heterocycle Quinolinone Electrophilic aromatic substitution |
| url | http://www.sciencedirect.com/science/article/pii/S2211715625000724 |
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