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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Detalles Bibliográficos
Autores principales: Shmidt, M.S., Arroyo Mañez, P., Stortz, C.A., Perillo, I.A., Vega, D., Blanco, M.M.
Formato: JOUR
Materias:
4-Quinolones
Alkylation
B3LYP
DFT
Regioselectivity
Carboxylation
Chemical reactions
Isomers
Single crystals
X ray diffraction analysis
Alkylating reagents
Basic medium
Carboxylate groups
DFT calculation
N-alkylation
Transition state
Crystal structure
Acceso en línea:http://hdl.handle.net/20.500.12110/paper_00222860_v1128_n_p142_Shmidt
Aporte de:
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
Descripción
Sumario: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.

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