text new page (beta)
Spanish (pdf)
Article in xml format
Article references
Automatic translation
Send this article by e-mail
Permalink
Texto completo disponible sólo en PDF.
Services on Demand
Journal
Article
Indicators
-
Cited by SciELO -
Access statistics
Related links
-
Similars in
SciELO
Share
TIP. Revista especializada en ciencias químico-biológicas
Print version ISSN 1405-888X
TIP vol.9 n.1 Ciudad de México Jun. 2006
Artículos originales
Espectroscopía y teoría de la regioquímica en la nitración de las benzopiridinas
Spectroscopy and regiochemistry theory in the benzopyridines nitration
1Facultad de Química, División de Estudios de Posgrado, UNAM. Ciudad Universitaria, CP. 04510, México, D.F.
En la presente comunicación se da una explicación teórica de la regioquímica observada en la nitración de las benzopiridinas, así como de los rendimientos relativos de los productos obtenidos. Se hizo una revisión de los métodos de preparación y de la espectroscopia de los compuestos estudiados. Un estudio cuidadoso de los espectros de RMN de 1H reveló la existencia en estos nitro compuestos de puentes de hidrógeno, del tipo C-H--'0-N=0, localizándose el átomo de hidrógeno en la posición peri al grupo nitro. La presencia de estas ligaduras secundarias explica los corrimientos a campo bajo observados en las señales de (dichos protones. Se determinaron los espectros de masas de la 5-nitro- y de la 8-nitroquinolina y se proponen los mecanismos de fragmentación de las rupturas típicas.
Palabras Clave: Espectrometría de masas; nitroquinolinas; nitroisoquinolinas; puentes de hidrógeno; resonancia magnética nuclear
In this communication we provide a theoretical explanation to the regiochemistry in the nitration of the benzopyridines as well as to the relative yields of the obtained products.
A review of the preparation procedures of the compounds under study is given, as well as the related spectroscopy. A careful study of 1 H NMR spectra revealed the existence of hydrogen bonds in these compounds. They are of the type С-Η-0-N=0, the hydrogen being at peri position to the nitro group. The existence of these bonds explains the down-field shifts observed in the signals of the involved protons.
The mass spectra of 5-nitro- and 8-nitroquinoline were determined. The fragmentation mechanisms of the typical ruptures are advanced.
Key Words: Hydrogen bonds; mass spectrometry; nitroquinolines; nitroisoquinolines; nuclear magnetic resonance
Referencias
1. Dennis, N. Pyridines and their Benzo Derivatives: Reactivity of Substituents, en Katritzky, A.R., Rees, C.W. & Scriven, E.F.V., Eds. Comprehensive Heterocyclic Chemistry II, Vol. 5, p. 93 (Pergamon, Oxford, 1996). [ Links ]
2. Katritzky, A.R. & Taylor, R. Electrophilic Substitution of Heterocycles, en Advances in Heterocyclic Chemistry, Vol. 47, p. 369 (Academic Press, San Diego, 1990) . [ Links ]
3. Uff, B.C. Pyridines and their Benzo Derivatives: Reactivity of Substituents, en Katritzky, A.R. & Rees, C.W., Eds. Comprehensive Heterocyclic Chemistry, Vol. 2, Parte 2 A, p. 317 (Pergamon, Oxford, 1984). [ Links ]
4. Dyke, S.F. & Kinsman, R.G. Properties and Reactions of Isoquinolines, en Grethe, G., Ed., Isoquinolines, Parte 1, p. 32, en Weissberger, A. & Taylor, C., Eds. The Chemistry of Heterocyclic Compounds (J. Wiley, Nueva York, 1981). [ Links ]
5. Jones, G. The Physical and Chemical Properties of Quinoline, en Jones, G., Ed. Quinolines, Parte 1, p. 44, en Weissberger, A. & Taylor, C, Eds. The Chemistry of Heterocyclic Compounds (J.Wiley, Londres, 1977). [ Links ]
6. Weaver, W.M. Introduction of the Nitro Group into Aromatic Systems, en Feuer, H., Ed. The chemistry of the nitro and nitroso groups, Parte 2, p. 24, en Patai, S., Ed. The Chemistry of Functional Groups (Interscience, Nueva York, 1970). [ Links ]
7. Elderfield, R.C. The Chemistry of Quinoline, en Elderfield, R.C., Ed. Heterocyclic Compounds, Vol. 4, p. 264 (J. Wiley, Nueva York, 1952). [ Links ]
8. Gensler, W.J. Isoquinoline, en Elderfield, R.C, Ed. Heterocyclic Compounds, Vol. 4, p. 411 (J. Wiley, Nueva York, 1952). [ Links ]
9. Palmer, M.H. The Structure and Reactions of Heterocyclic Compounds, pp. 118,150 (E. Arnold, Londres, 1967). [ Links ]
10. Fieser, L.F. & Hershberg, E.B. 20-Methyl-4-azacholanthrene. J. Am. Chem.Soc.,62, 1640 (1940). [ Links ]
11. Dikshoorn, R.P. The preparation of 5- and 8-aminoquinolines. Rec. trav. chim., 48, 147 (1929). [ Links ]
12. Le Fevre, C.G. & Le Fevre, J.W. The Dipole Moments and Structures of Some Quinoline Derivatives. J. Chem. ,Soc, 1935,1470. [ Links ]
13. Dufton, S.F. The Hydrazines of Quinoline. J. Chem., Soc, 61, 783(1892). [ Links ]
14. Kaufmann, A. & Decker, H. Ueber die Nitrirung des Chinolins und seiner Mononitroderivate. Ber, 39, 3648 (1906). [ Links ]
15. Meigen, W., Garbs, H., Merkelbach, W. & Wichern, G. Condensation Products of Dinitrochlorbenzene and Aminoquinolines. J.prakt. Chem. (2), 77,472 (1908). [ Links ]
16. Manske, R.H.F. & Kulka, M. The Skraup Synthesis of Quinolines, en Adams, R. Ed., Organic Reactions, Vol. 7, p. 59 (J. Wiley, Nueva York, 1953). [ Links ]
17. Sharma, K.S., Kumari, Sh. & Singh, R.P. Condensed Heterocycles, XL ,Synthesis, 1981, 316. [ Links ]
18. Brown, R.D. & Harcourt, R.D. A Theoretical Treatment of the Chemistry of Quinoline. J. Chem., Soc, 1959, 3451. [ Links ]
19. Sandorfy, C. & Yvan, P. Comparaison entre les grandeurs caractérisant la réactivité chimique dans le cas de la pyridine et de la quinoléine. Bull. ,Soc. Chim. France, 17, 131(1950). [ Links ]
20. Dewar, M.J.S. & Maitlis, P.M. Nitration of SomeSix-membered Nitrogen-heterocyclic Compounds in Sulphuric Acid. Chem. Soc, 1957, 2521. [ Links ]
21. Pouchert, Ch. J., Ed. The Aldrich Library of FTTR Spectra, Edición I, Vol. 2, p. 865, espectro N2380-7. (Aldrich, Milwaukee, 1985). [ Links ]
22. Pretsch, E., Bulmann, P., Affolter, C, Herrera, A. & Martinez, R. Determinación estructural de compuestos orgánicos, p. 271 (Masson, Barcelona, 2002). [ Links ]
23. Referencia 21, p. 867. [ Links ]
24. Referencia 21, Vol. 1 p.7. [ Links ]
25. Referencia 22, p. 246. [ Links ]
26. Black, P.J. & Heffernan, M.L. The analysis of the proton magnetic resonance spectra of heteroaromatic systems. Austri Chem., 17, 558 (1964). [ Links ]
27. Kaiya, T., Shirai, N. & Kawazoe, Y. Proton and Carbon-13 Nuclear Magnetic Resonance Chemical Shift Data for Nitroquinolines and their TV-Oxides. Chem. Pharm. Bull, 34, 881 (1986). [ Links ]
28. Referencia 22, p. 195. [ Links ]
29. Armarego, W.L.F. & Batterham, T.J. Proton Magnetic Resonance Spectra of Some Di- and Tri-azanaphtalenes and Nitroisoquinolines. J. Chem. Soc, B, 1966, 750. [ Links ]
30. Sadder Standard Spectra, N.M.R. 6096M (Sadder Research Laboratories, Philadelphia, 1969). [ Links ]
31. Referencia 22, p.196. [ Links ]
32. Radt, F., Ed. Elsevier ' s Encyclopaedia of Organic Chemistry, Serie III, Carboisocyclic Condensed Compounds, Vol. 12 B, Naphthalene, p. 6 (Elsevier, Nueva York, 1948) . [ Links ]
33. Lucchini, V. & Wells, P.R. Proton Magnetic Resonance Spectra of Monosubstituted Naphtalenes. Org. Magn. Resonance, 8, 137(1976). [ Links ]
34. Perumal, S., Vasuki, G., Wilson, D.A. & Boykin, D.W. 1H, 13C and 17O NMR Spectral Study of 4,1-Disubstituted Naphthalenes. Magn. Res. in Chem., 30, 320 (1992). [ Links ]
35. Sánchez-Viesca, F. & Berros, M. 1HNMREvidence of C-H-0, C-H-N and C-H-СІ Hydrogen Bonds in NewThiazole Derivatives. Heterocycles, 57,1869 (2002). [ Links ]
36. Sánchez-Viesca, F., Berros, M. & Gómez, M.R. Intramolecular Weak Hydrogen Bonds in Substituted 4-Arylthiazoles. Heterocyclic Comm., 9,165 (2003). [ Links ]
37. Rao, C.N.R. Spectroscopy of the Nitro Group, en Feuer, H. Ed., The Chemistry of Nitro and Nitroso Groups. Parte I, p. 112 (J. Wiley, Nueva York, 1969). [ Links ]
38. Balakrishnan, P. & Boykin, D.W. Natural Abundance 17O NMR Spectroscopy of Heteroaromatic Nitro Compounds. J Heterocyclic Chem., 23, 191 (1986). [ Links ]
39. Balakrishnan, P. & Boykin, D.W. Relationship of Aromatic Nitro Group Torsion Angles with 17O Chemical Shift Data .J. Org. Chem., 50, 3661 (1985). [ Links ]
40. Forbes, W.F., Intramolecular hydrogen bonding and steric interactions in o-nitrobenzaldehyde and related compounds. Can.J. Chem., 40,1891 (1962). [ Links ]
41. Pinchas, S., Intramolecular hydrogen bonding in o-nitrobenzaldehyde and related compounds. J. Phys. Chem.67,1862 (1963). [ Links ]
42. Budzikiewicz, H, Djerassi, C. & Williams, D.H., Mass Spectrometry of Organic Compounds, p. 518 (Holden-Day, San Francisco, 1967) . [ Links ]
43. Ibidem, p. 515. [ Links ]
44. Lange, N.A., Ed., Handbook of Chemistry, 10a. ed., p. 345 (McGraw-Hill, Nueva York, 1961) . [ Links ]
45. Patterson, A.M., Capell, L.T., & Walker, D.F., The Ring Index, p.179 (American Chemical Society, Washington, 1960). [ Links ]
Recibido: 23 de Febrero de 2006; Aprobado: 18 de Mayo de 2006
Este es un artículo publicado en acceso abierto bajo una licencia Creative Commons
