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Abstract:

Overwhelming evidence has been previously reported for the existence of the so-called "dimer nucleophile mechanism" in aromatic nucleophilic substitutions by amines in aprotic solvents, for which the most prominent feature is the fourth-order kinetics (third order in amine) that has been observed with many different substrate-nucleophile systems, especially those in which departure of the nucleofuge is the rate-determining step. The mechanism has been confirmed by several other features, although other alternative mechanisms were suggested to explain the fourth-order kinetics, no one has been able to explain the other above-mentioned features. The present paper affords additional experimental evidence and derivation of the kinetic expressions for reactions with good nucleofugues, where the first step is rate determining. The work involves studies of the reactions of 2,4-dinitrofluorobenzene and 2,4-dinitrochlorobenzene with aniline and with alkyldiamines in toluene. The novelty of this work lies in the selection of substrate-nucleophile systems exhibiting kinetic behavior that allows estimations of the different k's involved. The satisfactory agreement between the quotients of k's calculated from sets of data obtained under different reaction conditions hereby reported indicates that the assumptions made are correct and that the whole treatment applied to the kinetic data is justified. All together, the results fit well with the reaction scheme involving the dimer nucleophile mechanism, adding new evidence to this mechanism that it is well established in the current literature. © 2010 Wiley Periodicals, Inc.

Registro:

Documento: Artículo
Título:The "dimer nucleophile mechanism" for reactions with rate-determining first step: Derivation of the whole kinetic law and further treatment of kinetic results
Autor:Alvaro, C.E.S.; Nudelman, N.S.
Filiación:Departamento de Química, Facultad de Ingeniería, Universidad Nacional Del Comahue, Buenos Aires 1400, (8300) Neuquén, Argentina
Departamento de Química Orgánica, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Pab. II, P 3 Ciudad Universitaria, (1428) Buenos Aires, Argentina
Palabras clave:Aprotic solvents; Aromatic nucleophilic substitution; Different substrates; Dimer nucleophile mechanisms; Dinitrochlorobenzene; Experimental evidence; Fourth-order; Kinetic behavior; Kinetic data; Kinetic expression; Kinetic law; Prominent features; Rate determining step; Reaction conditions; Reaction schemes; Third order; Organic compounds; Toluene; Nucleophiles
Año:2010
Volumen:42
Número:12
Página de inicio:735
Página de fin:742
DOI: http://dx.doi.org/10.1002/kin.20523
Título revista:International Journal of Chemical Kinetics
Título revista abreviado:Int J Chem Kinet
ISSN:05388066
CODEN:IJCKB
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_05388066_v42_n12_p735_Alvaro

Referencias:

  • Alvaro, C.E.S., Ayala, A.D., Nudelman, N.S., (2010) J Phys Org Chem, 23
  • Buncel, E., Dust, J.M., Terrier, F., (1995) Chem Rev, 95, p. 2261
  • Nudelman, N.S., (1996) The Chemistry of Amino, Nitroso, Nitro and Related Groups, pp. 1215-1300. , (a) In; Patai, S. (Ed.); Wiley J & Sons Ltd.: London,; Ch. 29, pp. , and references therein
  • Nudelman, N.S., Montserrat, J.M., (1990) J Chem Soc, Perkin Trans, 2, pp. 1073-1076
  • Hintermann, L., Masuo, R., Suzuki, K., (2008) Org Lett, pp. 4859-4862
  • Meenakshisundaram, S., Selvaraju, M., Made Gowda, N.M., Rangappa, K.S., (2005) Int J Chem Kinet, 37, pp. 649-657
  • Karunakaran, C., Kamalam, R., (2002) J Org Chem, 1118. , (b
  • Karunakaran, C., Palanisamy, P.N., (1999) Int J Chem Kinet, 31, p. 571. , (c
  • Banjoko, O., Babatunde, I., (2004) Tetrahedron, 60, pp. 4645-4654
  • Banjoko, O., Babatunde, I., (2005) Tetrahedron, pp. 8035-8040
  • Emokpae, T.A., Isanbor, C., (2004) Int J Chem Kinet, pp. 188-196
  • Emokpae, T.A., Atasie, N.V., (2005) Int J Chem Kinet, pp. 744-750
  • Bhuvaneshwari, D.S., Elango, K.P., (2006) Int J Chem Kinet, pp. 166-175
  • Bhuvaneshwari, D.S., Elango, K.P., (2006) Z Phys Chem, 220, pp. 697-721
  • Crampton, M.R., Emokpae, T.A., Howard, J.A.K., Isanbor, C., Mondal, R., (2004) J Phys Org Chem, pp. 65-70
  • Isanbor, C., Emokpae, T.A., Crampton, M.R., (2002) J Chem Soc, Perkin Trans, 2, pp. 2019-2024
  • Crampton, M.R., Emokpae, T.A., Isanbor, C., (2006) J Phys Org Chem, 19, pp. 75-80
  • Crampton, M.R., Emokpae, T.A., Isanbor, C., Batsanov, A.S., Howard, J.A.K., Mondal, R., (2006) Eur J Org Chem, 5, pp. 1222-1230
  • Crampton, M.R., Emokpae, T.A., Isanbor, C., (2007) Eur J Org Chem, 8, pp. 1378-1383
  • Gallardo, I., Guirado, G., (2008) Eur J Org Chem, 14, pp. 2463-2472
  • Al-Kaysi, R.O., Gallardo, I., Guirado, G., (2008) Int J Chem Kinet, 40, pp. 125-135
  • Reichardt, C., (2003) Solvent and Solvents Effects in Organic Chemistry, , In, 3rd ed.; Wiley-VCH, Verlag GmcH & Co. KgaA: Weinheim, Germany
  • Jacobsson, M., Oxgaard, J., Abrahamsson, C., Norrby, P., Goddard, W.A., Ellervik, U., (2008) Molecules, pp. 1282-1302
  • Alvaro, C.E.S., Nudelman, N.S., (2003) ARKIVOC, 10, pp. 95-106
  • Nudelman, N.S., Alvaro, C.E.S., Savini, M., Nicotra, V., Yankelevich, J.S., (1999) Collect Czech Chem Commun, 64, pp. 1583-1593
  • 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., Yankelevich, J.S., (1997) J Chem Soc, Perkin Trans 2, pp. 2125-2130
  • Mancini, P.M.E., Perez, A.D.C., Vottero, L.R., (2001) J Solution Chem, 30, pp. 695-707
  • Mancini, P.M.E., Fortunato, G., Adam, C., Vottero, L.R., Terenzani, A., (2002) J Phys Org Chem, 15, pp. 258-269
  • Mancini, P.M.E., Adam, C., Perez, A.D.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. , (a);, , and references cited therein
  • Forlani, L., Boga, C., Forconi, M., (1999) J Chem Soc Perkin Trans, 2, pp. 1455-1458
  • Bhuvaneshwari, D.S., Kalaimani, N., Rathinam, S., (2008) Indian J Chem, 17 A, pp. 1348-1354
  • Habibi-Yangjieh, A., Jafari-Tarzanag, Y., Banaei, A.R., (2009) Int J Chem Kinet, 41, pp. 153-159
  • Khodadadi-Moghaddam, M., Habibi-Yangjeh, A., Gholami, M.R., (2009) Monatsh Chem, 140, pp. 329-334
  • Rao, C.N., Pradeep, T., (1991) Chem Soc Rev, 20, p. 477
  • Desiraju, G.R., Steiner, T., (1999) The Weak Hydrogen Bond in Structural Chemistry and Biology, , (a); Oxford University Press: New York
  • Scheiner, S., (1997) Hydrogen Bonding: A Theorical Perspective, , (b); Oxford University Press: New York
  • Alvaro, C.E.S., Nudelman, N.S., (2005) J Phys Org Chem, 18, pp. 880-885. , and references therein
  • Raczynska, E.D., Maria, P.C., Gal, J.F., Decouzon, M., (1994) J Phys Org Chem, 7, pp. 725-733
  • Raczynska, E.D., Decouzon, M., Gal, J.F., Maria, P.C., Taft, R.W., Anvia, F., (2000) J Org Chem, 65, pp. 4635-4640

Citas:

---------- APA ----------
Alvaro, C.E.S. & Nudelman, N.S. (2010) . The "dimer nucleophile mechanism" for reactions with rate-determining first step: Derivation of the whole kinetic law and further treatment of kinetic results. International Journal of Chemical Kinetics, 42(12), 735-742.
http://dx.doi.org/10.1002/kin.20523
---------- CHICAGO ----------
Alvaro, C.E.S., Nudelman, N.S. "The "dimer nucleophile mechanism" for reactions with rate-determining first step: Derivation of the whole kinetic law and further treatment of kinetic results" . International Journal of Chemical Kinetics 42, no. 12 (2010) : 735-742.
http://dx.doi.org/10.1002/kin.20523
---------- MLA ----------
Alvaro, C.E.S., Nudelman, N.S. "The "dimer nucleophile mechanism" for reactions with rate-determining first step: Derivation of the whole kinetic law and further treatment of kinetic results" . International Journal of Chemical Kinetics, vol. 42, no. 12, 2010, pp. 735-742.
http://dx.doi.org/10.1002/kin.20523
---------- VANCOUVER ----------
Alvaro, C.E.S., Nudelman, N.S. The "dimer nucleophile mechanism" for reactions with rate-determining first step: Derivation of the whole kinetic law and further treatment of kinetic results. Int J Chem Kinet. 2010;42(12):735-742.
http://dx.doi.org/10.1002/kin.20523