Solvent effects on aromatic nucleophilic substitutions. Part 6. Kinetics of the reaction of 1‐chloro‐2, 4‐dinitrobenzene with piperidine in binary solvent mixtures

The kinetics of the reaction between 1-chloro-2,4-dinitrobenzene and piperidine was studied in several completely non-aqueous binary solvent mixtures where the preferential solvation is the rule at 15, 25 and 40°C. The reaction was chosen as the simplest example of aromatic nucleophilic substitutions (ANS). For (aprotic solvent + aprotic co-solvent) binary systems the co-solvent was toluene, and the rest of the solvents used were selected with different structural characteristics and an extensive range of polarity. In this kind of mixture a property of mixed binary solvents would be defined by means of ET(30) values and the solvent effects on this simple model of ANS reactions are similar to those of aprotic pure solvents, especially if hydrogen-bond donor solvent mixtures are excluded from the analysis. For (aprotic solvent + protic co-solvent) binary systems the co-solvent used was methanol. The presence of a protic solvent in the mixture strongly determines the solvent effects on the reaction. In this type of binary mixture, the chemical probe under consideration may not be generally valid to interpret solvation effects. Additionally, empirical solvent polarity parameters ET(30) were determined UV-VIS spectrophotometrically for some pure aprotic solvents and, as a function of the composition, for (dimethylformamide + toluene), (toluene + methanol) and (1,1,1-trichloroethane + methanol) at 15 and 40°C, with the purpose of extending the studies on the empirical polarity indices in binary solvent mixtures to the thermo-solvatochromic area.

[1]  P. Mancini,et al.  Determination of the empirical polarity parameter ET(30) for binary solvent mixtures , 1995 .

[2]  E. Bosch,et al.  Linear solvation energy relationships between electrolyte pK values and solvent properties for several 2‐methylpropan‐2‐Ol–cosolvent mixtures , 1994 .

[3]  C. Reichardt,et al.  Solvatochromic Dyes as Solvent Polarity Indicators , 1994 .

[4]  Y. Marcus.  Use of chemical probes for the characterization of solvent mixtures. Part 1. Completely non-aqueous mixtures , 1994 .

[5]  Russell S. Drago,et al.  A unified scale of solvent polarities for specific and non-specific interactions , 1994 .

[6]  Michael H. Abraham,et al.  Hydrogen bonding. 31. Construction of a scale of solute effective or summation hydrogen‐bond basicity , 1993 .

[7]  M. Abraham.  Application of solvation equations to chemical and biochemical processes , 1993 .

[8]  A. Blum,et al.  Solute/solvent interactions and their empirical determination by means of solvatochromic dyes , 1993 .

[9]  Y. Marcus,et al.  The properties of organic liquids that are relevant to their use as solvating solvents , 1994 .

[10]  W. Linert,et al.  Acceptor properties of solvents : the use of isokinetic relationships to elucidate the relationship between the acceptor number and the solvatochromism of N-phenolate betaine dyes , 1993 .

[11]  E. Bosch,et al.  Dissociation constants and preferential solvation in some 2-methylpropan-2-ol–alcohol mixtures , 1993 .

[12]  E. Bosch,et al.  Relationship between ET polarity and composition in binary solvent mixtures , 1992 .

[13]  Y. Marcus,et al.  Polarity and hydrogen-bonding ability of some binary aqueous–organic mixtures , 1991 .

[14]  Y. Marcus,et al.  Polarity, hydrogen bonding, and structure of mixtures of water and cyanomethane , 1991 .

[15]  Erwin Buncel,et al.  Solvatochromism and solvent polarity scales , 1990 .

[16]  E. Bosch,et al.  Ionic equilibria in neutral amphiprotic solvents: relationships between electrolyte pK values and solvent polarity and composition for several binary isopropyl alcohol mixtures , 1990 .

[17]  E. Buncel,et al.  Solvatochromic studies of novel azo merocyanine dyes. The .pi.*azo scale of solvent polarity , 1989 .

[18]  R. D. Martinez,et al.  Solvent effects on aromatic nucleophilic substitutions. Part 3. The kinetics of the reaction of 2,4-dinitrochlorobenzene with piperidine in aprotic solvents , 1984 .

[19]  C. Gardner Swain,et al.  Substituent and solvent effects on chemical reactivity , 1984 .

[20]  R. Taft,et al.  Linear solvation energy relationships. 26. Some measures of relative self-association of alcohols and water , 1983 .

[21]  Marguerite S. Swain,et al.  Solvent effects on chemical reactivity. Evaluation of anion- and cation-solvation components , 1983 .

[22]  R. Taft,et al.  Linear solvation energy relationships. 20. Intra- vs. intermolecular hydrogen bonding by some 2-nitroaniline and 2-nitrophenol derivatives , 1982 .

[23]  S. Balakrishnan,et al.  Empirical polarity parameters for some binary solvent mixtures , 1981 .

[24]  C. Reichardt.  Empirical Parameters of Solvent Polarity as Linear Free‐Energy Relationships , 1979 .

[25]  R. Taft,et al.  The solvatochromic comparison method. 6. The .pi.* scale of solvent polarities , 1977 .

[26]  C. F. Bernasconi,et al.  Changing views on the mechanism of base catalysis in nucleophilic aromatic substitution. Kinetics of reactions of nitroaryl ethers with piperidine and with n-butylamine in aqueous dioxane , 1977 .

[27]  J. Napier,et al.  THE NITROGEN HYPERFINE SPLITTING CONSTANT OF THE NITROXIDE FUNCTIONAL GROUP AS A SOLVENT POLARITY PARAMETER. THE RELATIVE IMPORTANCE FOR A SOLVENT POLARITY PARAMETER OF ITS BEING A CYBOTACTIC PROBE VS. ITS BEING A MODEL PROCESS , 1976 .

[28]  T. Krygowski,et al.  Complementary Lewis acid-base description of solvent effects. I. Ion-ion and ion-dipole interactions , 1975 .

[29]  J. Sinsheimer,et al.  Hydrogen-bond studies of the near infrared combination bands of the butylamines , 1974 .

[30]  D. Walther.  Untersuchungen zur Polarität organischer Lösungsmittel und filmbildender Polymere mit Hilfe der Solvatochromie von 1,2‐Diimin‐Komplexen des Molybdän(0) , 1974 .

[31]  J. Shorter.  Correlation analysis in organic chemistry : an introduction to linear free-energy relationships , 1973 .

[32]  N. B. Chapman,et al.  Advances in Linear Free Energy Relationships , 1972 .

[33]  J. Dubois,et al.  Influence des solvants sur la transition n → π: II. — Cétones saturées. Nouvelle méthode rigoureuse de calcul , 1968 .

[34]  E. Kosower.  An introduction to physical organic chemistry , 1968 .

[35]  H. Zollinǵer,et al.  Katalytische Effekte bei der nukleophilen aromatischen Substitution in Benzol 3. Mitteilung über nukleophilc aromatische Substitutionsreaktioncn , 1966 .

[36]  J. Bunnett,et al.  Base Catalysis of the Reaction of Piperidine with 2,4-Dinitrophenyl Phenyl Ether. Further Substantiation of the Intermediate Complex Mechanism for Aromatic Nucleophilic Substitution1 , 1965 .

[37]  L. Brooker,et al.  Color and Constitution. XIII.1 Merocyanines as Solvent Property Indicators2 , 1965 .

[38]  C. Reichardt.  Empirical Parameters of the Polarity of Solvents , 1965 .

[39]  S. Ross,et al.  Nucleophilic Displacement Reactions in Aromatic Systems. VII. The ortho:para Ratio in the Reactions of Nitrochlorobenzenes with Piperidine and with 1,4-Diazabicyclo(2.2.2)octane , 1963 .

[40]  P. Schleyer,et al.  Solvent Effects in Infrared Spectroscopic Studies of Hydrogen Bonding , 1963 .

[41]  W. Greizerstein,et al.  The ortho:para Ratio in the Activation of the Nucleophilic Aromatic Substitution by the Nitro Group , 1962 .

[42]  S. Brownstein.  THE EFFECT OF SOLVENTS UPON EQUILIBRIA, SPECTRA, AND REACTION RATES , 1960 .

[43]  M. Newman,et al.  Steric Effects In Organic Chemistry , 1956 .

[44]  J. Bunnett,et al.  The Rates of Condensation of Piperidine with 1-Chloro-2,4-dinitrobenzene in Various Solvents , 1955 .

[45]  J. Bunnett,et al.  The ortho: para Ratio in Activation of Aromatic Nucleophilic Substitution by the Nitro Group1 , 1955 .