Alkylation of 2- and 3-alkoxycarbonyl-4-quinolinones. DFT study on the regioselectivity
The reaction of 2-alkoxycarbonyl-4-quinolinones (1) with a variety of alkylating reagents under different conditions, lead to the corresponding O-alkylated products. The behavior in basic medium of compounds 1 differs from the 3-alkoxycarbonyl-4-quinolinones (4) isomers suggesting that the position...
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todo:paper_00222860_v1128_n_p142_Shmidt2023-10-03T14:30:31Z Alkylation of 2- and 3-alkoxycarbonyl-4-quinolinones. DFT study on the regioselectivity Shmidt, M.S. Arroyo Mañez, P. Stortz, C.A. Perillo, I.A. Vega, D. Blanco, M.M. 4-Quinolones Alkylation B3LYP DFT Regioselectivity Alkylation Carboxylation Chemical reactions Isomers Regioselectivity Single crystals X ray diffraction analysis 4-Quinolones Alkylating reagents B3LYP Basic medium Carboxylate groups DFT calculation N-alkylation Transition state Crystal structure The reaction of 2-alkoxycarbonyl-4-quinolinones (1) with a variety of alkylating reagents under different conditions, lead to the corresponding O-alkylated products. The behavior in basic medium of compounds 1 differs from the 3-alkoxycarbonyl-4-quinolinones (4) isomers suggesting that the position of the carboxylate group determines the regioselectivity of the reaction. DFT calculations allow us to conclude that for 3-alkoxycarbonyl-4-quinolinones, the N-alkylation would be thermodynamically and kinetically favored. But for 2-alkoxycarbonyl-4-quinolinones the side chain in the 2-position of the ring prevents the planar approximation to the contiguous heteroatom leading to a more favorable O-alkylation transition state. Crystal structure of an O-alkylated product is determined by single crystal X-ray diffractometry. © 2016 Elsevier B.V. Fil:Arroyo Mañez, P. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Stortz, C.A. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_00222860_v1128_n_p142_Shmidt |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
4-Quinolones Alkylation B3LYP DFT Regioselectivity Alkylation Carboxylation Chemical reactions Isomers Regioselectivity Single crystals X ray diffraction analysis 4-Quinolones Alkylating reagents B3LYP Basic medium Carboxylate groups DFT calculation N-alkylation Transition state Crystal structure |
| spellingShingle |
4-Quinolones Alkylation B3LYP DFT Regioselectivity Alkylation Carboxylation Chemical reactions Isomers Regioselectivity Single crystals X ray diffraction analysis 4-Quinolones Alkylating reagents B3LYP Basic medium Carboxylate groups DFT calculation N-alkylation Transition state Crystal structure Shmidt, M.S. Arroyo Mañez, P. Stortz, C.A. Perillo, I.A. Vega, D. Blanco, M.M. Alkylation of 2- and 3-alkoxycarbonyl-4-quinolinones. DFT study on the regioselectivity |
| topic_facet |
4-Quinolones Alkylation B3LYP DFT Regioselectivity Alkylation Carboxylation Chemical reactions Isomers Regioselectivity Single crystals X ray diffraction analysis 4-Quinolones Alkylating reagents B3LYP Basic medium Carboxylate groups DFT calculation N-alkylation Transition state Crystal structure |
| description |
The reaction of 2-alkoxycarbonyl-4-quinolinones (1) with a variety of alkylating reagents under different conditions, lead to the corresponding O-alkylated products. The behavior in basic medium of compounds 1 differs from the 3-alkoxycarbonyl-4-quinolinones (4) isomers suggesting that the position of the carboxylate group determines the regioselectivity of the reaction. DFT calculations allow us to conclude that for 3-alkoxycarbonyl-4-quinolinones, the N-alkylation would be thermodynamically and kinetically favored. But for 2-alkoxycarbonyl-4-quinolinones the side chain in the 2-position of the ring prevents the planar approximation to the contiguous heteroatom leading to a more favorable O-alkylation transition state. Crystal structure of an O-alkylated product is determined by single crystal X-ray diffractometry. © 2016 Elsevier B.V. |
| format |
JOUR |
| author |
Shmidt, M.S. Arroyo Mañez, P. Stortz, C.A. Perillo, I.A. Vega, D. Blanco, M.M. |
| author_facet |
Shmidt, M.S. Arroyo Mañez, P. Stortz, C.A. Perillo, I.A. Vega, D. Blanco, M.M. |
| author_sort |
Shmidt, M.S. |
| title |
Alkylation of 2- and 3-alkoxycarbonyl-4-quinolinones. DFT study on the regioselectivity |
| title_short |
Alkylation of 2- and 3-alkoxycarbonyl-4-quinolinones. DFT study on the regioselectivity |
| title_full |
Alkylation of 2- and 3-alkoxycarbonyl-4-quinolinones. DFT study on the regioselectivity |
| title_fullStr |
Alkylation of 2- and 3-alkoxycarbonyl-4-quinolinones. DFT study on the regioselectivity |
| title_full_unstemmed |
Alkylation of 2- and 3-alkoxycarbonyl-4-quinolinones. DFT study on the regioselectivity |
| title_sort |
alkylation of 2- and 3-alkoxycarbonyl-4-quinolinones. dft study on the regioselectivity |
| url |
http://hdl.handle.net/20.500.12110/paper_00222860_v1128_n_p142_Shmidt |
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