Experimental and GIAO 15N NMR study of substituent effects in 1 H -tetrazoles
A series of 1-aryl/alkyl-1H-1,2,3,4-tetrazoles, 5-substituted 1H-tetrazoles, and 1,5- and 2,5-disubstituted 1H-tetrazoles were studied by a combination of experimental NMR (natural abundance 15N, 15N/ 1H HMBC, and 13C) and computational GIAO-NMR techniques to explore substituent effects on 15N (and...
| Autores: | , , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2012 |
| País: | Argentina |
| Institución: | Consejo Nacional de Investigaciones Científicas y Técnicas |
| Repositorio: | CONICET Digital (CONICET) |
| Idioma: | inglés |
| OAI Identifier: | oai:ri.conicet.gov.ar:11336/62479 |
| Acceso en línea: | http://hdl.handle.net/11336/62479 |
| Access Level: | acceso abierto |
| Palabra clave: | 15n Nmr Tetrazoles Substituent Effects https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
| Sumario: | A series of 1-aryl/alkyl-1H-1,2,3,4-tetrazoles, 5-substituted 1H-tetrazoles, and 1,5- and 2,5-disubstituted 1H-tetrazoles were studied by a combination of experimental NMR (natural abundance 15N, 15N/ 1H HMBC, and 13C) and computational GIAO-NMR techniques to explore substituent effects on 15N (and 13C) NMR chemical shifts in the tetrazole (TA) moiety. Computed 15N chemical shifts via GIAO-B3LYP/6-311+G(2d,p) calculations gave satisfactory results in comparison with experimental data. Whereas N-alkylation leads to large 15N chemical shift changes, changes in the N 1-aryl derivatives bearing diverse substituent(s) are generally small except for polar ortho-substituents (COOH, NO 2). Large δδ 15N values were computed in N 1-aryl derivatives for p-COH 2 + and p-OMeH + as extreme examples of electron-withdrawing substituents on a TA moiety. © 2012 American Chemical Society. |
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