As misturas binárias de solventes têm sido profusamente e desde há muito tempo utilizadas em estudos de reactividade e por essa razão não existe propriamente uma divisão clara entre trabalhos em solventes puros e misturas. No entanto, pode dizer-se que existem essencialmente duas formas de utilização das misturas em estudos de reactividade:
i. - ou são elas próprias o objecto de estudo e a reactividade de substratos tipo é utilizada como método de caracterização dinâmico da mistura, e é neste tipo de análise que este trabalho se insere, bem como o de vários grupos de investigação [73- 79].
ii. - ou o objecto de estudo é o substrato e nesse caso o que se procura obter é uma informação cinético-mecanística usando as misturas de forma a conseguir um “controlo” do processo por variação do(s) parâmetro(s) caracterizador(es) do meio solvente, conseguido através da variação da percentagem de cada um dos componentes. Um exemplo evidente desta aplicação são as relações de Grunwald- Winstein [38] discutidas no próximo capítulo, e que utilizam como solvente de referência a mistura 80% v/v etanol/água.
Paralelamente, e igualmente importante, tal como se referiu no capítulo I, é a utilização das misturas por razões de ordem prática, nomeadamente em estudos em
consequentemente o tempo de reacção é excessivamente longo) ou apresenta problemas experimentais (solubilidade, reactividade secundária, etc.). A metodologia neste caso envolve a utilização de várias misturas com outro solvente em que o problema experimental não ocorre, e deste modo e com um número suficiente de fracções molares é possível construir uma função de ajuste matemático e extrapolar o valor “experimental” pretendido. A desvantagem deste tipo de abordagem é o facto de implicar a realização de um maior número de ensaios e, se a extrapolação ocorrer a partir de fracções molares demasiado distantes do valor a determinar, o erro associado ser potencialmente maior.
Bibliografia
1. Reichardt, C., Solvents and Solvent Effects in Organic Chemistry. 3rd ed., Wiley-VCH: Weinheim, 2003.
2. Atkins, P.W.; De Paula, J., Atkins' Physical Chemistry. 7th ed.,Oxford University Press: Oxford ; New York, 2002.
3. Laidler, K.J.; King, M.C., The Development of Transition-State Theory. Journal
of Physical Chemistry, 1983, 87(15), 2657-2664.
4. Truhlar, D.G.; Hase, W.L.; Hynes, J.T., Current Status of Transition-State Theory. Journal of Physical Chemistry, 1983, 87(15), 2664-2682.
5. Eyring, H., The Activated Complex in Chemical Reactions. Journal of Chemical
Physics, 1935, 3(2), 107-115.
6. Evans, M.G.; Polanyi, M., Some Applications of the Transition State Method to the Calculation of Reaction Velocities, Especially in Solution. Transactions of
the Faraday Society, 1935, 31(1), 0875-0893.
7. Albuquerque, L.M.P.C., Efeitos da Temperatura e da Pressão na Cinética de
Reacções de Solvólise em Etilenoglicol e Glicerol, Tese de Doutoramento,
Universidade de Lisboa, Lisboa, 1979.
8. Gonçalves, R.M.C., Análise Termodinâmica de Reacções de Solvólise em iso-
Propanol e Butanol Terciário, Tese de Doutoramento, Universidade de Lisboa,
Lisboa, 1978.
9. Leitão, F.E.L.M.E., Estudo Mecanistico da Reacção do 2-Iodo-2-Metil-Propano
Com Metanol, Tese de Doutoramento, Universidade de Lisboa, Lisboa, 1993.
10. Simões, A.M.N., Estudo Cinético e Mecanístico de Reacções de Alcoólise de 2-
Cloro e 2-Bromo-2-Metilpropano, Tese de Doutoramento, Universidade de
Lisboa Lisboa, 1986.
11. Baskin, J.S.; Zewail, A.H., Freezing Atoms in Motion: Principles of Femtochemistry and Demonstration by Laser Stroboscopy. Journal of Chemical
Education, 2001, 78(6), 737-751.
12. Albuquerque, L.C.; Moita, L.C.; Simões, A.N.; Gonçalves, R.C.; Macedo, E.A., Kinetic and Thermodynamic Study of 2-Bromo-2-Methylbutane, 2-Chloro-2- Methylbutane and 3-Chloro-3-Methylpentane in Diols. Journal of Physical
Organic Chemistry, 1998, 11(1), 36-40.
13. Albuquerque, L.C.; Simões, A.N.; Ventura, C.M.; Gonçalves, R.C.; Macedo, E.A., Infinite Dilution Activity Coefficients Predicted from UNIFAC Model. New Experimental Data for the Solvolytic Reactions of 2-Chloro-2-Methylpropane in Methanol/Ethanol, Methanol/2-Methoxyethanol, and Ethanol/2-Methoxyethanol.
Industrial & Engineering Chemistry Research, 1996, 35(10), 3759-3762.
14. Abraham, M.H., Solvent Effects on Reaction-Rates. Pure and Applied
Chemistry, 1985, 57(8), 1055-1064.
15. Abraham, M.H.; Grellier, P.L.; Nasehzadeh, A.; Walker, R.A.C., Substitution at Saturated Carbon .26. A Complete Analysis of Solvent Effects on Initial States and Transition-States for the Solvolysis of the tert-Butyl Halides in Terms of G, H, and S Using the Unified Method. Journal of the Chemical Society-Perkin
Transactions 2, 1988(9), 1717-1724.
16. Macedo, E.A.; Gonçalves, R.C.; Simões, A.N.; Ventura, C.M.; Albuquerque, L.C., Infinite Dilution Activity-Coefficients from Unifac Model for 2-Chloro-2- Methylpropane in Binary-Mixtures of Alcohols - Application to the Mechanistic Study of Solvolytic Reactions. Industrial & Engineering Chemistry Research,
1995, 34(5), 1910-1913.
17. Gonçalves, R.M.C.; Simões, A.M.N.; Albuquerque, L.M.P.C.; Macedo, E.A., Study of Initial-State and Transition-State Solvation in the Solvolysis of tert- Butyl Halides in Alcohols from Infinite Dilution Activity-Coefficients. Journal of
18. Gonçalves, R.M.C.; Calado, A.R.T.; Pinheiro, L.M.V.; Albuquerque, L.M.P.C.; Macedo, E.A., Study of Initial-State and Transition-State Solvation in the Menschutkin Reaction of Triethylamine with Ethyl Iodide in Alcohols from Infinite Dilution Activity-Coefficients. Journal of Physical Organic Chemistry,
1993, 6(10), 595-599.
19. Huh, C.; Lee, H.W.; Lee, I., The Measurement of Transfer Enthalpy in Mixed- Solvent .2. Solvent Effects on Nucleophilic-Substitution Reactions of Ethyl and 2-Phenylethyl Benzenesulfonates. Bulletin of the Korean Chemical Society,
1995, 16(1), 53-58.
20. Ingold, C.K., Principles of an Electronic Theory of Organic Reactions. Chemical
Reviews, 1934, 15(2), 225-274.
21. Gonçalves, R.M.C.; Martins, F.E.L., A Further View on the Methanolysis of tert- Butyl Iodide - a Conductimetric and Spectrophotometric Study. Anales De
Quimica, 1990, 86(7), 694-699.
22. Gonçalves, R.M.C.; Martins, F.E.L.; Simões, A.M.N., Reactions of tert-Butyl Halides with Straight Chain Alcohols - a Mechanistic Approach. Anales De
Quimica, 1992, 88(4), 417-420.
23. Martins, F.; Leitão, R.E.; Moreira, L., Solvation Effects in the Heterolyses of 3- X-3-Methylpentanes (X = Cl, Br, I). Journal of Physical Organic Chemistry,
2004, 17(11), 1061-1066.
24. Hughes, E.D.; Ingold, C.K., Mechanism of Substitution at a Saturated Carbon Atom. Part IV. A Discussion of Constitutional and Solvent Effects on the Mechanism, Kinetics, Velocity, and Orientation of Substitution. Journal of the
Chemical Society, 1935, 244-255.
25. Abraham, M.H., Advances in Solution Chemistry, Bertini, I.;Lunazzi, L.;Dei, A., Editores., Plenum Press, New York, 1981.
26. Winstein, S.; Clippinger, E.; Fainberg, A.H.; Heck, R.; Robinson, G.C., Salt Effects and Ion Pairs in Solvolysis and Related Reactions .3. Common Ion Rate Depression and Exchange of Anions During Acetolysis. Journal of the American
Chemical Society, 1956, 78(2), 328-335.
27. Tsuji, Y.; Richard, J.P., When Does an Intermediate Become a Transition State? Degenerate Isomerization without Competing Racemization During Solvolysis of (S)-1-(3-Nitrophenyl)Ethyl Tosylate. Journal of the American
Chemical Society, 2006, 128(51), 17139-17145.
28. McManus, S.P.; Somani, S.; Harris, J.M.; McGill, R.A., A Solvolysis Model for 2- Chloro-2-Methyladamantane Based on the Linear Solvation Energy Approach.
Journal of Organic Chemistry, 2004, 69(25), 8865-8873.
29. Minegishi, S.; Loos, R.; Kobayashi, S.; Mayr, H., Kinetics of the Reactions of Halide Anions with Carbocations: Quantitative Energy Profiles for S(N)1 Reactions. Journal of the American Chemical Society, 2005, 127(8), 2641- 2649.
30. Carey, F.A.; Sundberg, R.J., Advanced Organic Chemistry. 5th ed,Springer, New York, 2007.
31. Ventura, M.C.M.M., Caracterização Estática e Reaccional de Misturas Binárias
Álcool/Álcool e Álcool/Alcoxiálcool, Tese de Doutoramento, Universidade de
Lisboa, Lisboa, 2001.
32. Dvorko, G.F.; Koshchii, I.V.; Ponomareva, E.A., Solvation and Conformational Effects in Heterolysis of 1-Methylcycloalkyl Halides. Theoretical and
Experimental Chemistry, 2003, 39(2), 99-103.
33. Muller, P.; Rossier, J.C.; Abboud, J.L.M., Gas-Phase Stability of Tertiary Carbenium Ions and Rates of Solvolysis of Tertiary Derivatives. Journal of
Physical Organic Chemistry, 2000, 13(10), 569-573.
34. Abboud, J.L.M.; Alkorta, I.; Davalos, J.Z.; Muller, P.; Quintanilla, E.; Rossier, J.C., Influence of Carbocation Stability in the Gas Phase on Solvolytic
Reactivity: Beyond Bridgehead Derivatives. Journal of Organic Chemistry,
2003, 68(10), 3786-3796.
35. Abboud, J.L.M.; Castano, O.; Della, E.W.; Herreros, M.; Muller, P.; Notario, R.; Rossier, J.C., Correlation of Gas-Phase Stability of Bridgehead Carbocations with Rates of Solvolysis and Ab Initio Calculations. Journal of the American
Chemical Society, 1997, 119(9), 2262-2266.
36. Takeuchi, K.; Ohga, Y.; Ushino, T.; Takasuka, M., Structural Effects on the Grunwald-Winstein Correlations in the Solvolysis of Some Simple Tertiary Alkyl Chlorides. Journal of Physical Organic Chemistry, 1997, 10(10), 717-724. 37. Liu, K.T.; Hou, S.J.; Tsao, M.L., B-Strain and Solvolytic Reactivity Revisited.
Nucleophilic Solvent Participation and Abnormal Rate Ratios for Tertiary Chloroalkanes. Journal of Organic Chemistry, 1998, 63(4), 1360-1362.
38. Grunwald, E.; Winstein, S., The Correlation of Solvolysis Rates. Journal of the
American Chemical Society, 1948, 70(2), 846-859.
39. Winstein, S.; Grunwald, E.; Jones, H.W., The Correlation of Solvolysis Rates and the Classification of Solvolysis Reactions into Mechanistic Categories.
Journal of the American Chemical Society, 1951, 73(6), 2700-2707.
40. Koppel, I.A.; Palm, V.A., Advances in Linear Free Energy Relatioships, Chapman, N.B.;Shorter, J., Editores., Plenum Press, London, 1972 p. 202. 41. Abraham, M.H.; Taft, R.W.; Kamlet, M.J., Linear Solvation Energy Relationships
.15. Heterolytic Decomposition of the tert-Butyl Halides. Journal of Organic
Chemistry, 1981, 46(15), 3053-3056.
42. Gonçalves, R.M.C.; Simões, A.M.N.; Leitão, R.A.S.E.; Albuquerque, L.M.P.C., Correlation of Rate Constants for the Solvolysis of tert-Butyl Halides - Effect of Temperature. Journal of Chemical Research-S, 1992(10), 330-331.
43. Gonçalves, R.M.C.; Simões, A.M.N.; Albuquerque, L.M.P.C., Linear Solvation- Energy Relationships - Solvolytic Reactions of tert-Butyl Bromide and tert-Butyl Iodide in Hydroxylic Solvents. Journal of the Chemical Society-Perkin
Transactions 2, 1990(8), 1379-1383.
44. Gajewski, J.J., Is the tert-Butyl Chloride Solvolysis the Most Misunderstood Reaction in Organic Chemistry? Evidence against Nucleophilic Solvent Participation in the tert-Butyl Chloride Transition State and for Increased Hydrogen Bond Donation to the 1-Adamantyl Chloride Solvolysis Transition State. Journal of the American Chemical Society, 2001, 123(44), 10877-10883. 45. Farcasiu, D.; Jahme, J.; Ruchardt, C., Relative Reactivity of Bridgehead
Adamantyl and Homoadamantyl Substrates from Solvolyses with
Heptafluorobutyrate as a Highly Reactive Carboxylate Leaving Group - Absence of SN2 Character of Solvolysis of tert-Butyl Derivatives. Journal of the
American Chemical Society, 1985, 107(20), 5717-5722.
46. Dvorko, G.F.; Ponomareva, E.A.; Ponomarev, M.E., Role of Nucleophilic Solvation and the Mechanism of Covalent Bond Heterolysis. Journal of Physical
Organic Chemistry, 2004, 17(10), 825-836.
47. Dvorko, G.F.; Zaliznyi, V.V.; Ponomarev, N.E., Kinetics and Mechanism of Monomolecular Heterolysis of Commercial Organohalogen Compounds: XXX. Correlation Analysis of Solvation Effects in Heterolysis of tert-Butyl Chloride.
Russian Journal of General Chemistry, 2002, 72(10), 1549-1555.
48. Dvorko, G.F.; Koshchii, I.V.; Ponomareva, E.A., Kinetics and Mechanism of Monomolecular Heterolysis of Commercial Organohalogen Compounds: XXXVI. Solvent Effect on the Activation Parameters of Heterolysis of 1-Methyl- 1-Chlorocyclohexane. Correlation Analysis of Solvation Effects in Heterolysis of 1-Methyl-1-Chlorocyclohexane and 1-Methyl-1-Chlorocyclopentane. Russian
Journal of General Chemistry, 2003, 73(4), 569-574.
49. Dvorko, G.F.; Koshchii, I.V.; Prokopets, A.M.; Ponomareva, E.A., Kinetics and Mechanism of Monomolecular Heterolysis of Commercial Organohalogen Compounds: XXXII. Solvent Effects on Activation Parameters of Heterolysis of
1-Chloro-1-Methylcyclopentane. Correlation Analysis of Solvation Effects.
Russian Journal of General Chemistry, 2002, 72(12), 1882-1893.
50. Dvorko, G.F.; Koshchii, I.V.; Ponomareva, E.A., Kinetics and Mechanism of Monomolecular Heterolysis of Commercial Organohalogen Compounds:
XXXIV. Solvent Effect on the Heterolysis Rate of 1-Chloro-1-
Methylcyclohexane. Correlation Analysis of Solvation Effects in Heterolysis of 1- Chloro-1-Methylcyclohexane and 1-Chloro-1-Methylcyclopentane. Russian
Journal of General Chemistry, 2003, 73(2), 204-212.
51. Ponomarev, N.E.; Stambirskii, A.V.; Dvorko, G.F., Kinetics and Mechanism of Monomolecular Heterolysis of Commercial Organohalogen Compounds: XXVIII. Effect of the Nature of the Verdazyl Indicator on Salt Effects in Dehydrobromination of 3-Bromocyclohexene in Nitrobenzene. Russian Journal
of General Chemistry, 2002, 72(1), 79-85.
52. Dvorko, G.F.; Zaliznyi, V.V.; Ponomarev, N.E., Kinetics and Mechanism of Monomolecular Heterolysis of Commercial Organohalogen Compounds: XXIX. Solvent Effects on the Activation Parameters of Heterolysis of tert-Butyl Chloride. Russian Journal of General Chemistry, 2002, 72(9), 1414-1428. 53. Dvorko, G.F.; Koshchii, I.V.; Prokopets, A.M.; Ponomareva, E.A., Kinetics and
Mechanism of Monomolecular Heterolysis of Commercial Organohalogen
Compounds: XXXI. Solvent Effect on the Rate of 1-Methyl-1-
Chlorocyclopentane Heterolysis. Correlation Analysis of Solvation Effects.
Russian Journal of General Chemistry, 2002, 72(11), 1797-1804.
54. Dvorko, G.F.; Koshchii, I.V.; Ponomareva, E.A., Kinetics and Mechanism of Monomolecular Heterolysis of Commercial Organohalogen Compounds: XXXIII. Correlation Analysis of Solvation Effects in Monomolecular Heterolysis of 1- Bromo-1-Methylcyclopentane, 1-Bromo-1-Methylcyclohexane, and 2-Bromo-2- Methyladamantane. Russian Journal of General Chemistry, 2003, 73(1), 104- 113.
55. Dvorko, G.F.; Koshchii, I.V.; Ponomareva, E.A., Kinetics and Mechanism of Monomolecular Heterolysis of Commercial Organohalogen Compounds: XXXV. Solvation Effects on the Activation Parameters of Heterolysis of 1-Bromo-1- Methylcyclopentane and 1-Bromo-1-Methylcyclohexane. Correlation Analysis of Solvation Effects. Russian Journal of General Chemistry, 2003, 73(3), 375-388. 56. Dvorko, G.F.; Koshchii, I.V.; Ponomareva, E.A., Kinetics and Mechanism of
Monomolecular Heterolysis of Commercial Organohalogen Compounds: XXXVII. Effect of Nucleofuge and Solvent of the Relative Rates of Heterolysis of 1-Halo-1-Methylcyclopentanes and 1-Halo-1-Methylcyclohexanes. Correlation Analysis of Solvation Effects. Russian Journal of General Chemistry, 2003, 73(9), 1426-1433.
57. Raber, D.J.; Bingham, R.C.; Harris, J.M.; Fry, J.L.; Schleyer, P.V., Role of Solvent in Solvolysis of tert-Alkyl Halides. Journal of the American Chemical
Society, 1970, 92(20), 5977-5981.
58. Schadt, F.L.; Bentley, T.W.; Schleyer, P.V.R., SN2-SN1 Spectrum .2. Quantitative Treatments of Nucleophilic Solvent Assistance - Scale of Solvent Nucleophilicities. Journal of the American Chemical Society, 1976, 98(24), 7667-7674.
59. Bentley, T.W.; Carter, G.E., The SN2-SN1 Spectrum .4. The Sn2 (Intermediate) Mechanism for Solvolyses of tert-Butyl Chloride - a Revised Y-Scale of Solvent Ionizing Power Based on Solvolyses of 1-Adamantyl Chloride. Journal of the
American Chemical Society, 1982, 104(21), 5741-5747.
60. Kevill, D.N.; Dsouza, M.J., Additional Y(Cl) Values and the Correlation of the Specific Rates of Solvolysis of tert-Butyl Chloride in Terms of N(T) and Y(Cl) Scales. Journal of Chemical Research-S, 1993(5), 174-175.
61. Abraham, M.H.; Doherty, R.M.; Kamlet, M.J.; Harris, J.M.; Taft, R.W., Linear Solvation Energy Relationships .38. An Analysis of the Use of Solvent
Parameters in the Correlation of Rate Constants, with Special Reference to the Solvolysis of tert-Butyl Chloride. Journal of the Chemical Society-Perkin
Transactions 2, 1987(8), 1097-1101.
62. Abraham, M.H.; Doherty, R.M.; Kamlet, M.J.; Harris, J.M.; Taft, R.W., Linear Solvation Energy Relationships .37. An Analysis of Contributions of Dipolarity Polarizability, Nucleophilic Assistance, Electrophilic Assistance, and Cavity Terms to Solvent Effects on tert-Butyl Halide Solvolysis Rates. Journal of the
Chemical Society-Perkin Transactions 2, 1987(7), 913-920.
63. Takeuchi, K.; Takasuka, M.; Shiba, E.; Kinoshita, T.; Okazaki, T.; Abboud, J.L.M.; Notario, R.; Castano, O., Experimental and Theoretical Evaluation of Energetics for Nucleophilic Solvent Participation in the Solvolysis of Tertiary Alkyl Chlorides on the Basis of Gas Phase Bridgehead Carbocation Stabilities.
Journal of the American Chemical Society, 2000, 122(30), 7351-7357.
64. Takeuchi, K.; Takasuka, M.; Shiba, E.; Tokunaga, H.; Endo, T.; Ushino, T.; Tokunaga, K.; Okazaki, T.; Kinoshita, T.; Ohga, Y., The Grunwald-Winstein Relationship in the Solvolysis of Crowded Tertiary Alkyl Chlorides. Hindered Hydration and Hydrophobic Effect. Journal of Physical Organic Chemistry,
2001, 14(4), 229-238.
65. Takeuchi, K., Structural Modification and Solvent Interactions in Solvolytic Reactions of Open-Chain Compounds. Pure and Applied Chemistry, 1998, 70(10), 2023-2030.
66. Abboud, J.L.M.; Herreros, M.; Notario, R.; Lomas, J.S.; Mareda, J.; Muller, P.; Rossier, J.C., The Stability of Bridgehead Carbocations. Journal of Organic
Chemistry, 1999, 64(17), 6401-6410.
67. Catalán, J.; Diaz, C.; Garcia-Blanco, F., Correlation of Solvolysis Rates 50 Years Later. Journal of Organic Chemistry, 1999, 64(17), 6512-6514.
68. Albuquerque, L.M.P.C.; Moita, M.L.C.J.; Gonçalves, R.M.C., Kinetics and Mechanisms of Solvolysis of 3-Chloro-3-Ethylpentane in Alcohols as Solvents. Application of Multiparametric Equations and Factor Analysis to the Solvolytic Reactions of tert-Alkyl Halides. Journal of Physical Organic Chemistry, 2001, 14(3), 139-145.
69. Richard, J.P.; Toteva, M.M.; Amyes, T.L., What Is the Stabilizing Interaction with Nucleophilic Solvents in the Transition State for Solvolysis of Tertiary Derivatives: Nucleophilic Solvent Participation or Nucleophilic Solvation?
Organic Letters, 2001, 3(14), 2225-2228.
70. Richard, J.P.; Jagannadham, V.; Amyes, T.L.; Mishima, M.; Tsuno, Y., A Comparison of Substituent Effects on the Stability of Alpha,Alpha- Dimethylbenzyl Carbocations in Aqueous-Solution and in the Gas-Phase - How Significant Is Nucleophilic Solvation. Journal of the American Chemical Society,
1994, 116(15), 6706-6712.
71. Bentley, T.W.; Garley, M.S., Correlations and Predictions of Solvent Effects on Reactivity: Some Limitations of Multi-Parameter Equations and Comparisons with Similarity Models Based on One Solvent Parameter. Journal of Physical
Organic Chemistry, 2006, 19(6), 341-349.
72. Reis, M.C.; Elvas-Leitão, R.; Martins, F., The Influence of Carbon-Carbon Multiple Bonds on the Solvolyses of Tertiary Alkyl Halides: A Grunwald- Winstein Analysis. International Journal of Molecular Sciences, 2008, 9(9), 1704-1716.
73. Mancini, P.M.; Fortunato, G.G.; Vottero, L.R., Kinetics of the Reactions between 1-Fluoro-2,6-Dinitrobenzene and Pyrrolidine and Piperidine in Binary Solvent Systems: Influence of the Nucleophile Structure. Journal of Physical Organic
Chemistry, 2004, 17(2), 138-147.
74. Mancini, P.M.; Terenzani, A.; Adam, C.; Pérez, A.D.; Vottero, L.R., Characterization of Solvent Mixtures: Preferential Solvation of Chemical Probes in Binary Solvent Mixtures of Polar Hydrogen-Bond Acceptor Solvents with
Polychlorinated Co-Solvents. Journal of Physical Organic Chemistry, 1999, 12(9), 713-724.
75. Mancini, P.M.E.; Terenzani, A.; Adam, C.; Pérez, A.; Vottero, L.R., Characterization of Solvent Mixtures. Part 8 - Preferential Solvation of Chemical Probes in Binary Solvent Systems of a Polar Aprotic Hydrogen-Bond Acceptor Solvent with Acetonitrile or Nitromethane. Solvent Effects on Aromatic Nucleophilic Substitution Reactions. Journal of Physical Organic Chemistry,
1999, 12(3), 207-220.
76. Mancini, P.M.E.; Terenzani, A.; Adam, C.; Vottero, L.R., Solvent Effects on Aromatic Nucleophilic Substitution Reactions .7. Determination of the Empirical Polarity Parameter ET(30) for Dipolar Hydrogen Bond Acceptor-Co-Solvent
(Chloroform or Dichloromethane) Mixtures. Kinetics of the Reactions of Halonitrobenzenes with Aliphatic Amines. Journal of Physical Organic
Chemistry, 1997, 10(11), 849-860.
77. Mancini, P.M.E.; Terenzani, A.; Adam, C.; Vottero, L.R., Solvent Effects on Aromatic Nucleophilic Substitution Reactions. Part 9. Special Kinetic Synergistic Behavior in Binary Solvent Mixtures. Journal of Physical Organic Chemistry,
1999, 12(6), 430-440.
78. Harati, M.; Gholami, M.R., Solute-Solvent Interaction Effects on Second-Order Rate Constants of Reaction between 1-Chloro-2,4-Dinitrobenzene and Aniline in Alcohol-Water Mixtures. International Journal of Chemical Kinetics, 2005, 37(2), 90-97.
79. Bhuvaneshwari, D.S.; Elango, K.P., Solvent Hydrogen Bonding and Structural Effects on Nucleophilic Substitution Reactions: Part 3. Reaction of Benzenesulfonyl Chloride with Anifines in Benzene/Propanp-2-ol Mixtures.