Navegar

Colección

Datos Estadísticas

Artículo

La versión final de este artículo es de uso interno. El editor solo permite incluir en el repositorio el artículo en su versión post-print. Por favor, si usted la posee enviela a
Consulte el artículo en la página del editor
Consulte la política de Acceso Abierto del editor

Abstract:

The kinetics of the reactions between 1-halogeno-2,4-dinitrobenzene (halogen = F, C1) and the amines ethylenediamine (EDA) and 3-dimethylamino-1- propylamine (DMPA) were studied in toluene at 25° ±0.2C under pseudo-first-order conditions using varying amounts of amine. Even with C1 as the nucleofugue (where usually the first step is rate-determining), a third-order-in-amine kinetic law was observed: these results can be interpreted within the 'dimer nucleophile' mechanism where the amine homo-aggregates are better nucleophiles than the amine monomers. To confirm this interpretation, the reaction of 2,4-dinitrofluorobenzene with histamine was studied in the same solvent. Because of the rigid geometry, an intramolecular hydrogen bond is easily established, which prevents the formation of self-aggregates. Consequently, the plot of kA vs. [histamine] is a straight line, as expected for a classical mechanism of base-catalysed decomposition of the zwitterionic intermediate. All these results are well explained in the frame of the 'dimer nucleophile' mechanism. Copyright © 2005 John Wiley & Sons, Ltd.

Registro:

Documento: Artículo
Título:Role of hydrogen-bonded nucleophiles in aromatic nucleophilic substitutions in aprotic solvents. Reactions of halonitrobenzenes with ethylenediamine, 3-dimethylamino-1-propylamine and histamine in toluene
Autor:Alvaro, C.E.S.; Nudelman, N.S.
Filiación:Departamento de Química, Facultad de Ingeniería, Universidad Nacional del Comahue, 8300 Neuquen, Buenos Aires 1400, Argentina
Departamento de Química Orgánica, Facultad de Ciencias Exactas y Naturales, P 3 Ciudad Universitaria, (1428), Buenos Aires, Argentina
Palabras clave:Aprotic solvents; Aromatic nucleophilic substitution; Dimer nucleophile mechanism; Hydrogen bond; Hydrogen-bonded nucleophiles; Mixed aggregates; Dimers; Hydrogen bonds; Molecular structure; Solvents; Substitution reactions; Surface treatment; Synthesis (chemical); Aprotic solvents; Aromatic nucleophilic substitution; Dimer nucleophile mechanisms; Hydrogen-bonded nucleophiles; Mixed aggregates; Aromatic compounds
Año:2005
Volumen:18
Número:8
Página de inicio:880
Página de fin:885
DOI: http://dx.doi.org/10.1002/poc.957
Título revista:Journal of Physical Organic Chemistry
Título revista abreviado:J Phys Org Chem
ISSN:08943230
CODEN:JPOCE
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_08943230_v18_n8_p880_Alvaro

Referencias:

  • Desiraju, G., Steiner, T., (1999) The Weak Hydrogen Bond, , Oxford University Press: New York
  • Scheiner, S., (1997) Hydrogen Bonding, , Oxford University Press: New York
  • Filarowski, A., Koll, A., Karpfen, A., Wolschann, P., (2004) Chem. Phys., 297, pp. 323-332
  • Ki Rhee, S., Hoon Kim, S., Lee, S., Young Lee, J., (2004) Chem. Phys., 297, pp. 21-29
  • Katritzky, A.R., Fara, D.C., Yang, H., Tämm, K., Tamm, T., Karelson, M., (2004) Chem. Rev., 104, pp. 175-198
  • Palm, N., Palm, V., (2000) Russ. J. Org. Chem., 36, p. 1075
  • Reichardt, C., (1994) Chem. Rev., 94, p. 2319
  • Abboud, J.-L.M., Notario, R., (1999) Pure Appl. Chem., 71, pp. 645-718
  • Marcus, Y., (1993) Chem. Soc. Rev., 22, pp. 409-416
  • Raczynska, E.D., Wozniak, K., (1998) Trends Org. Chem., 7, pp. 159-172
  • Zou, J.-W., Yu, Q.-S., Shang, Z.-C., (2000) Wuji Huaxue Xuebao, 58, p. 1247
  • Zou, J.-W., Shang, Z.-C., Yu, Q.-S., (2001) Wuji Huaxue Xuebao, 14, p. 51
  • Zhao, W.-N., Shang, Z.-C., Zou, J.-W., Guo, M., Yu, Q.-S., (2002) Wuji Huaxue Xuebao, 18, p. 726
  • Katritzky, A., Tamm, T., Wang, Y., Sild, S., Karelson, M., (1999) J. Chem. Inf. Comput. Sci., 39, p. 684
  • Spange, S., Vilsmeier, E., Fischer, K., Reuter, A., Prause, S., Zimmermann, Y., Schmidt, Ch., (2000) Macromol. Rapid Commun., 21, p. 643
  • Terrier, F., Nucleophile aromatic displacement: The influence of the Nitro group (1991) Organic Nitro Chemistry Series, , Ferrer H (ed). VCH Publishers: New York
  • Nudelman, N.S., (1996) The Chemistry of Amino, Nitroso, Nitro and Related Groups, pp. 1215-1300. , Patai S (ed). Wiley: Chichester
  • Nudelman, N.S., Savini, M., Alvaro, C.E.S., Nicotra, V., Yankelevich, J.S., (1999) J. Chem. Soc. Perkin Trans. 2, pp. 1627-1630
  • Nudelman, N.S., Alvaro, C.E.S., Savini, M., Nicotra, V., Yankelevich, J.S., (1999) Collect. Czech. Chem. Commun., 64, pp. 1583-1593
  • Mancini, P.M.E., Fortunato, G., Adam, C., Vottero, L.R., Terenzani, A.J., (2002) J. Phys. Org. Chem., 15, pp. 258-269
  • Mancini, P.M.E., Adam, C., Perez, A., Del, C., Vottero, L.R., (2000) J. Phys. Org. Chem., 13, pp. 221-231
  • Boga, C., Forlani, L., (2001) J. Chem. Soc. Perkin Trans. 2, pp. 1408-1413
  • Forlani, L., Boga, C., Forconi, M., (1999) J. Chem. Soc. Perkin Trans. 2, pp. 1455-1458
  • Nudelman, N.S., (1989) J. Phys. Org. Chem., 2, pp. 1-14
  • Chiacchiera, S.M., Singh, J.O., Anunziata, J.D., Silver, J.J., (1988) J. Chem. Soc. Perkin Trans. 2, pp. 1585-1589
  • Forlani, L., (1996) The Chemistry of Amino, Nitroso, Nitro and Related Groups, pp. 423-477. , Patai S (ed). Wiley: Chichester
  • Forlani, L., (1999) J. Phys. Org. Chem., 12, pp. 417-424
  • Sugiyama, N., Hayami, J., (1999) Chem. Soc. Jpn., pp. 691-692
  • Rao, C.N., Pradeep, T., (1991) Chem. Soc. Rev., 20, p. 477
  • Ramondo, F., Bencivenni, L., Portalone, G., Domenicano, A., (1994) Struct. Chem., 5, p. 1
  • Llamas-Saiz, A.L., Foces-Foces, C., Elguero, J., (1994) J. Mol. Struct., 328, p. 297
  • Nudelman, N.S., Palleros, D., (1981) Acta Sud. Am. Quim., 1, p. 125
  • Nudelman, N.S., Palleros, D., (1983) J. Org. Chem., 48, p. 1607
  • Hirst, J., (1994) J. Phys. Org. Chem., 7, p. 68
  • Nudelman, N.S., Montserrat, J.M., (1990) J. Chem. Soc. Perkin Trans. 2, pp. 1073-1076
  • Nudelman, N.S., Alvaro, C.E.S., Yankelevich, J.S., (1997) J. Chem. Soc. Perkin Trans. 2, pp. 2125-2130
  • Weast, R.C., (1977) Handbook of Chemistry and Physics (57th Edn), , CRC Press, Inc: Cleveland, Ohio, USA
  • Nudelman, N.S., Marder, M., Gurevich, A., (1993) J. Chem. Soc. Perkin Trans. 2, pp. 229-233
  • Vogel, A., (1978) Practical Organic Chemistry (4th Edn), p. 526. , Longman Inc: New York, USA
  • Bunnet, J.F., Kato, T., Nudelman, N.S., (1974) Fundamental Organic Chemistry Laboratory Manual, p. 112. , Finley KT, Wilson J (eds). Prentice-Hall: New Jersey

Citas:

---------- APA ----------
Alvaro, C.E.S. & Nudelman, N.S. (2005) . Role of hydrogen-bonded nucleophiles in aromatic nucleophilic substitutions in aprotic solvents. Reactions of halonitrobenzenes with ethylenediamine, 3-dimethylamino-1-propylamine and histamine in toluene. Journal of Physical Organic Chemistry, 18(8), 880-885.
http://dx.doi.org/10.1002/poc.957
---------- CHICAGO ----------
Alvaro, C.E.S., Nudelman, N.S. "Role of hydrogen-bonded nucleophiles in aromatic nucleophilic substitutions in aprotic solvents. Reactions of halonitrobenzenes with ethylenediamine, 3-dimethylamino-1-propylamine and histamine in toluene" . Journal of Physical Organic Chemistry 18, no. 8 (2005) : 880-885.
http://dx.doi.org/10.1002/poc.957
---------- MLA ----------
Alvaro, C.E.S., Nudelman, N.S. "Role of hydrogen-bonded nucleophiles in aromatic nucleophilic substitutions in aprotic solvents. Reactions of halonitrobenzenes with ethylenediamine, 3-dimethylamino-1-propylamine and histamine in toluene" . Journal of Physical Organic Chemistry, vol. 18, no. 8, 2005, pp. 880-885.
http://dx.doi.org/10.1002/poc.957
---------- VANCOUVER ----------
Alvaro, C.E.S., Nudelman, N.S. Role of hydrogen-bonded nucleophiles in aromatic nucleophilic substitutions in aprotic solvents. Reactions of halonitrobenzenes with ethylenediamine, 3-dimethylamino-1-propylamine and histamine in toluene. J Phys Org Chem. 2005;18(8):880-885.
http://dx.doi.org/10.1002/poc.957