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Abstract:

The kinetics of the reaction of 2,4-dinitrochlorobenzene with aniline have been studied in toluene and in toluene-methanol binary solvents and compared with the reactions in benzene and chloroform. The reactions in aprotic solvents exhibit a rate dependence that is third-order in amine consistent with aggregates of the aniline acting as the nucleophile. Molecular complexes between the aniline and the substrate were also detected spectrophotometrically. Additionally, an inhibitory effect of toluene complexes was observed, which is similar to the previously reported effect of benzene in the reaction of the same substrate with n-butylamine. The reaction in the presence of pyridine shows an amine dependence which indicates formation of 'mixed aggregates' between aniline and pyridine. All the above results, as well as recently reported studies of other reactions different from SNAr, are fully interpreted within the 'dimer nucleophile' mechanism.

Registro:

Documento: Artículo
Título:Aggregation effects in the reactions of 2,4-dinitrochlorobenzene with aniline in aprotic solvents
Autor:Nudelman, N.S.; Alvaro, C.E.S.; Yankelevich, J.S.
Filiación:Depto. de Química, Facultad de Ingeniería, Universidad Nacional del Comahue, Neuquén, Argentina
Depto. Quim. Orgánica, Fac. de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Pab. II, P. 3, 1428 Buenos Aires, Argentina
Año:1997
Número:10
Página de inicio:2125
Página de fin:2130
DOI: http://dx.doi.org/10.1039/a607108b
Título revista:Journal of the Chemical Society. Perkin Transactions 2
Título revista abreviado:J Chem Soc Perkin Trans 2
ISSN:03009580
CODEN:JCPKB
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_03009580_v_n10_p2125_Nudelman

Referencias:

  • Lambert, C., Von Schleyer, P.R., (1952) Methoden Org. Chem. (Houben-Weyl), 4th Ed, E19D, p. 1
  • Trost, B.M., Fleming, I., (1991) Comprehensive Organic Synthesis, 1. , Pergamon Press, Oxford
  • Nudelman, N.S., Lewkowicz, E., Furlong, J.J.P., (1993) J. Org. Chem., 58, p. 1847
  • Decouzon, M., Gal, J.F., María, P.C., Raczynska, E.D., (1993) Rapid Commun. Mass Spectrom., 7, p. 599
  • Koppel, I.A., Anvia, F., Taft, R.W., (1994) J. Phys. Org. Chem., 7, p. 717
  • Berthelot, M., Helbert, M., Laurence, C., LeQuestel, J.Y., Anvia, F., Taft, R.W., (1993) J. Chem. Soc., Perkin Trans. 2, p. 625
  • Koppel, I.A., Molder, U.H., Pikver, R.J., (1991) Electron and Proton Affinities of Molecules, pp. 5-112. , URSS Academy of Sciences Press, Ufa
  • Meot-Ner, M., Sieck, L.W., (1991) J. Am. Chem. Soc., 113, p. 4448
  • Bordwell, F.G., Hughes, D.L., (1986) J. Am. Chem. Soc., 108, p. 5991
  • Gandler, J.R., Setiarahardjo, I.U., Tufon, C., Chen, C., (1992) J. Org. Chem., 57, p. 4169
  • Reichardt, C.F., (1988) Solvents and Solvent Effects in Organic Chemistry, 2nd Edn., , VCH, Weinheim
  • Koppel, I.A., Taft, R.W., Anvia, F., Zhu, S.Z., Hu, L.Q., Sung, K.S., DesMarteau, D.D., Maria, P.C., (1994) J. Am. Chem. Soc., 116, p. 3047
  • Chechick, V.O., Bobylev, V.A., (1993) Zh Obshch, Khim., 63, p. 1502
  • Headley, A.D., Strarness, S.D., Cheung, E.T., Malone, P.L., (1995) J. Phys. Org. Chem., 8, p. 26
  • Gupta, S., (1987) Chem. Rev., 87, p. 1183
  • Jeffrey, G.A., Saenger, W., (1991) Hydrogen Bonding in Biological Molecules, , Springer-Verlag, Berlin-Heidelberg
  • Tamaru, K., Ichikama, M., (1975) Catalysis by Electron-Donor-Acceptor Complexes, , Wiley, New York
  • Nudelman, N.S., (1996) SNAr by Amines in Dipolar Aprotic Solvents in the Chemistry of Amino, Nitroso, Nitro and Related Groups, , ed. S. Patai, Wiley, Chichester, in press
  • Forlani, L., Bosi, M., (1992) J. Phys. Org. Chem., 5, p. 429. , and references therein
  • Durantini, E., Zingaretti, L., Anunziata, J.D., Silber, J.J.J., (1992) Phys. Org. Chem., 5, p. 557. , and references therein
  • Forlani, L., (1982) Gazz. Chim. Ital., 112, p. 205
  • Nudelman, N.S., Palleros, D.R., (1983) J. Org. Chem., 48, p. 1613
  • Nudelman, N.S., Palleros, D.R., (1985) J. Chem. Soc., Perkin Trans. 2, p. 479
  • Bunnett, J.F., Kato, T., Nudelman, N.S., (1974) Fundamental Organic Chemistry Laboratory Manual, p. 112. , ed. K. T. Finley and J. Wilson, Prentice-Hall, New Jersey
  • Nudelman, N.S., Marder, M., Gurevich, A., (1993) J. Chem. Soc., Perkin Trans. 2, p. 229. , and references therein
  • Nudelman, N.S., (1989) J. Phys. Org. Chem., 2, p. 1. , and references therein
  • Hirst, J., (1995) J. Phys. Org. Chem., 7, p. 68. , and references therein
  • Dixon, J.E., Bruice, T.C., (1972) J. Am. Chem. Soc., 94, p. 2052
  • Nudelman, N.S., Palleros, D.R., (1983) J. Org. Chem., 48, p. 1607
  • Nudelman, N.S., Montserrat, J., (1990) J. Chem. Soc., Perkin Trans. 2, p. 1073
  • Terrier, F., Nucleophilic Aromatic Displacement: The influence of the nitro group (1991) Organic Nitro Chemistry Series, , ed. H. Ferrer, VCH Publishers, New York
  • Chiacchiera, S.M., Singh, J.O., Anunziata, J.D., Silber, J.J., (1988) J. Chem. Soc., Perkin Trans. 2, p. 1585
  • Bunnett, J.F., Morath, (1955) J. Am. Chem. Soc., 77, p. 5051
  • Mancini, P.M., Martinez, R.D., Vottero, L.R., Nudelman, N.S., (1984) J. Chem. Soc., Perkin Trans. 2, p. 1133
  • Martinez, R.D., Mancini, P.M., Vottero, L.R., Nudelman, N.S., (1986) J. Chem. Soc., Perkin Trans. 2, p. 1427
  • Mancini, P.M., Terenzani, A., Gasparri, M.G., Vottero, L.R., (1995) J. Phys. Org. Chem., 8, p. 617
  • Nudelman, N.S., Savini, M., Nicotra, V., Yankelevich, J., unpublished work; Hirst, J., Onuoha, G.N., Onyido, Y., (1988) J. Chem. Soc., Perkin Trans. 2, p. 971
  • Forlani, L., Todesco, P.E., (1980) Gazz. Chim. Ital., 100, p. 561
  • V. Frena, G. Vivona, G. Consiglio and D. Spinelli, 1985, 2, 1865; Nudelman, N.S., Mancini, P.M., Martinez, R.D., Vottero, L.R., (1987) J. Chem. Soc., Perkin Trans. 2, p. 951
  • Persson, J., Axelsson, S., Matsson, O., (1996) J. Am. Chem. Soc., 118, p. 20
  • Johnson, J.E., Dutson, S.M., Dolliver, D.D., Todd, S.L., Hotema, M., (1995) J. Phys. Org. Chem., 8, p. 344
  • Gesser, J.C., Zucco, C., Nome, F., (1995) J. Phys. Org. Chem., 8, p. 97
  • Perepichka, I.F., Popov, A.F., (1995) J. Chem. Soc., Perkin Trans. 2, p. 3
  • Perepichka, I.F., Popov, A.F., Kostenko, L.I., Artyomova, T.V., Kovac, J., (1988) Chemistry of Heterocyclic Compounds, p. 462. , ed. J. Kovác and P. Zálupsky, Elsevier, Amsterdam
  • Perepichka, I.F., Kostenko, L.I., Popov, A.F., Chervinskii, A.Yu., (1988) Zh. Org. Khim., 24, p. 822

Citas:

---------- APA ----------
Nudelman, N.S., Alvaro, C.E.S. & Yankelevich, J.S. (1997) . Aggregation effects in the reactions of 2,4-dinitrochlorobenzene with aniline in aprotic solvents. Journal of the Chemical Society. Perkin Transactions 2(10), 2125-2130.
http://dx.doi.org/10.1039/a607108b
---------- CHICAGO ----------
Nudelman, N.S., Alvaro, C.E.S., Yankelevich, J.S. "Aggregation effects in the reactions of 2,4-dinitrochlorobenzene with aniline in aprotic solvents" . Journal of the Chemical Society. Perkin Transactions 2, no. 10 (1997) : 2125-2130.
http://dx.doi.org/10.1039/a607108b
---------- MLA ----------
Nudelman, N.S., Alvaro, C.E.S., Yankelevich, J.S. "Aggregation effects in the reactions of 2,4-dinitrochlorobenzene with aniline in aprotic solvents" . Journal of the Chemical Society. Perkin Transactions 2, no. 10, 1997, pp. 2125-2130.
http://dx.doi.org/10.1039/a607108b
---------- VANCOUVER ----------
Nudelman, N.S., Alvaro, C.E.S., Yankelevich, J.S. Aggregation effects in the reactions of 2,4-dinitrochlorobenzene with aniline in aprotic solvents. J Chem Soc Perkin Trans 2. 1997(10):2125-2130.
http://dx.doi.org/10.1039/a607108b