Spectroscopic and theoretical study in substituted N-phenoxyethylanilines |
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| Affiliation: | 1. Catedra de Fisicoquı́mica II, Facultad de Ciencias Exactas, 47 y 115, Universidad Nacional de La Plata, 1900 La Plata, Argentina;2. Laboratorio Nacional de Investigación y Servicios en Espectroscopı́a Óptica, Centro CEQUINOR, Departamento de Quı́mica and Departamento de Fı́sica, Universidad Nacional La Plata, CC 962, 1900 La Plata, Argentina;3. Laboratorio de Estudio de Compuestos Orgánicos, LADECOR, Departamento de Quı́mica, Universidad Nacional de La Plata, 1900 La Plata, Argentina;1. Department of Chemistry, University of North Carolina, Chapel Hill, NC 27599-3290, USA;2. Instituto de Quimica-Fisica ‘Rocasolano’, CSIC, Serrano 119, 28006 Madrid, Spain;1. Laboratorio de Servicios a la Industria y al Sistema Cientı´fico (UNLP-CIC-CONICET), Departamento de Química, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, 47 esq. 115, (1900) La Plata, Argentina;2. Institute of Pharmacy and Molecular Biotechnology, University of Heidelberg, Im Neuenheimer Feld 364, D-69120 Heidelberg, Germany;3. Max Planck Institute for Bioinorganic Chemistry, Stiftstraße 34–36, D-45470 Mülheim an der Ruhr, Germany;4. CEQUINOR (UNLP-CONICET), Departamento de Química, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, 47 esq. 115, (1900) La Plata, Argentina |
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| Abstract: | ![]()
Infrared spectroscopic studies, assigned with the aid of density functional calculations, and ab initio theoretical calculations of N-(2-phenoxyethyl)aniline and their derivatives allow us to have an insight into the vibrational, geometrical and electronic properties of N-(2-phenoxyethyl)aniline, N-(2-(4-nitrophenoxy)ethyl)aniline, 4-methoxy-N-(2-(4-chlorophenoxy)ethyl) aniline, 4-methoxy-N-(2-(2-nitrophenoxy)ethyl)aniline and 4-bromo-N-(2-(2-bromo-4-chlorophenoxy)ethyl)aniline. Our calculations indicate that the gauche conformation around the (CH2)2 chain is the lowest-energy for all the molecules.We further investigated the vibrational behavior of N-(2-phenoxyethyl)aniline, N-(2-(4-nitrophenoxyethyl)aniline and 4-methoxy-N-(2-(4-chlorophenoxy)ethyl)aniline compounds at 300 and 77 K where several peaks corresponding to normal modes associated with the lineal chain showed reinforcement and loosening of their force constants. The peak corresponding to N–H stretching mode has been found dependent on their position and intensity upon the substituents and derivatives. We find that the splitting at 3413–3381 and 3403–3374 cm−1 of the N–H band in the spectra of the NO2 derivatives cannot be associated with the existence of a conformational equilibrium, but may be assigned to a free N–H and to a NH⋯O bonded form, respectively.An analysis of the Mulliken charges on the atoms that constitute the aliphatic chain of the different compounds shows a difference on the acidic capacity of the hydrogen atom attached to the nitrogen atom. |
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