Structure of 1,5-benzodiazepinones in the solid state and in solution: Effect of the fluorination in the six-membered ring

Two novel tetrafluorinated 1,5-benzodiazepinones were synthesized and their X-ray structures determined. 6,7,8,9-Tetrafluoro-4- methyl-1,3-dihydro-2H-1,5-benzodiazepin-2-one crystallizes in the monoclinic P21/c space group and 6,7,8,9-tetrafluoro-1,4- dimethyl-1,3-dihydro-2H-1,5-benzodiazepin-2-one...

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Detalles Bibliográficos
Autores: Pérez-Torralba, Marta, Claramunt, Rosa M., García, M. Ángeles, López, Concepción, Torralba, M. Carmen, Torres, M. Rosario, Alkorta, Ibon, Elguero, José
Tipo de recurso: artículo
Fecha de publicación:2013
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/89134
Acceso en línea:http://hdl.handle.net/10261/89134
Access Level:acceso abierto
Palabra clave:Benzodiazepinones
DFT
GIAO calculations
inversion barriers
multinuclear NMR
tautomerism
X-ray structures
Descripción
Sumario:Two novel tetrafluorinated 1,5-benzodiazepinones were synthesized and their X-ray structures determined. 6,7,8,9-Tetrafluoro-4- methyl-1,3-dihydro-2H-1,5-benzodiazepin-2-one crystallizes in the monoclinic P21/c space group and 6,7,8,9-tetrafluoro-1,4- dimethyl-1,3-dihydro-2H-1,5-benzodiazepin-2-one in the triclinic P−1 space group. Density functional theory studies at the B3LYP/6-311++G(d,p) level were carried out on these compounds and on four non-fluorinated derivatives, allowing to calculate geometries, tautomeric energies and ring-inversion barriers, that were compared with the experimental results obtained by static and dynamic NMR in solution and in solid state.