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Abstract:

Investigations were carried out applying NMR spectroscopy for the unambiguous determination of the position of the N-oxide function in a set of 2-substituted pyrazine N-oxides synthesized in our group. Applying chemometric techniques of multivariate analysis to the 13C NMR chemical shifts data set, useful relationships for identifying the position of the N-oxide group relative to the substituent were unraveled. The relationships obtained were rationalized in terms of the molecular structures and refined. As a result, an index of N-oxidation (INOx) was defined, computed simply contrasting the average 13C NMR chemical shifts of each pair of carbon atoms bonded to a nitrogen atom. The effect of the substituent was included through a factor x (subscript of INO) close to unity, multiplying the average containing the substituted carbon atom. The approach was successful in recognizing the position of the N-oxide in all the cases studied, as revealed by the sign of INOx (positive for 1-N-oxides and negative for 4-N-oxides). The scope of the methodology was further tested using the 13C NMR chemical shifts of disubstituted pyrazine N-oxides from the literature data. © 2013 Elsevier B.V. All rights reserved.

Registro:

Documento: Artículo
Título:Determination of the position of the N-O function in substituted pyrazine N-oxides by chemometric analysis of carbon-13 nuclear magnetic resonance data
Autor:Butler, M.; Cabrera, G.M.
Filiación:Departamento de Química Orgánica, Universidad de Buenos Aires, Ciudad Universitaria, C1428EHA Buenos Aires, Argentina
Palabras clave:13C; Chemometric analysis; NMR; Position of N-oxide; Pyrazine N-oxides; Structure elucidation; 13C; Chemometric analysis; N-Oxides; Position of N-oxide; Structure elucidation; Atoms; Chemical shift; Nuclear magnetic resonance; Nuclear magnetic resonance spectroscopy; Carbon
Año:2013
Volumen:1043
Página de inicio:37
Página de fin:42
DOI: http://dx.doi.org/10.1016/j.molstruc.2013.03.058
Título revista:Journal of Molecular Structure
Título revista abreviado:J. Mol. Struct.
ISSN:00222860
CODEN:JMOSB
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00222860_v1043_n_p37_Butler

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Citas:

---------- APA ----------
Butler, M. & Cabrera, G.M. (2013) . Determination of the position of the N-O function in substituted pyrazine N-oxides by chemometric analysis of carbon-13 nuclear magnetic resonance data. Journal of Molecular Structure, 1043, 37-42.
http://dx.doi.org/10.1016/j.molstruc.2013.03.058
---------- CHICAGO ----------
Butler, M., Cabrera, G.M. "Determination of the position of the N-O function in substituted pyrazine N-oxides by chemometric analysis of carbon-13 nuclear magnetic resonance data" . Journal of Molecular Structure 1043 (2013) : 37-42.
http://dx.doi.org/10.1016/j.molstruc.2013.03.058
---------- MLA ----------
Butler, M., Cabrera, G.M. "Determination of the position of the N-O function in substituted pyrazine N-oxides by chemometric analysis of carbon-13 nuclear magnetic resonance data" . Journal of Molecular Structure, vol. 1043, 2013, pp. 37-42.
http://dx.doi.org/10.1016/j.molstruc.2013.03.058
---------- VANCOUVER ----------
Butler, M., Cabrera, G.M. Determination of the position of the N-O function in substituted pyrazine N-oxides by chemometric analysis of carbon-13 nuclear magnetic resonance data. J. Mol. Struct. 2013;1043:37-42.
http://dx.doi.org/10.1016/j.molstruc.2013.03.058