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ARTICLE pubs.acs.


The Cosolvent-Directed DielsÀAlder Reaction in Ionic Liquids
Nageshwar D Khupse and Anil Kumar*
Physical Chemistry Division, National Chemical Laboratory, Pune 411 008, India
S Supporting Information b

ABSTRACT: The rate constants of a bimolecular DielsÀAlder reaction in binary mixtures of ionic liquids prepared in molecular solvents were analyzed to investigate the effect of viscosity of the medium and solvent effect. In this connection, we have carried out the DielsÀAlder reaction of anthracene 9-carbinol with N-ethyl maleimide in binary mixtures of pyridinium-based ionic liquids, 1-butyl-pyridinium tetrafluoroborate, 1-butyl-3-pyridinium tetrafluoroborate, and 1-butyl-4-methyl pyridinium tetrafluoroborate in water, methanol, and chloroform at 298.15 K. The rates of reaction decreased, caused by gradually increasing the volume fraction of ionic liquids in solvents for all three ionic liquids. The kinetic results demonstrate a successful application of the pairwise interaction model built upon the concept of enforced hydrophobic hydration. A temperature-dependent study of kinetics of the DielsÀAlder reaction was carried out in the binary mixtures of ionic liquids in water and was explained by the entropyÀenthalpy compensation effect based upon activation parameters. Kinetics of the DielsÀAlder reaction in highly aqueous medium was noted to be entropically driven.

’ INTRODUCTION In recent years, room temperature ionic liquids have been used as catalyst to realize several organic reactions. Ionic liquids have recently been considered as an alternative to replace volatile organic solvents in chemical processes, because of their special interesting physicochemical properties.1À4 Ionic liquids possess insignificant vapor pressures, are nonflammable, and can dissolve different types of compounds. Their physical properties may be tuned by varying the structures of their ions. Out of several reactions, the DielsÀAlder reaction is one of the important CÀC bond forming reactions used for manufacturing six-membered rings with fine control over stereoselectivities of the products.5 The DielsÀAlder reactions normally should exhibit small solvent effects in organic solvents due to the presence of isopolar activated complex.6 However, the rate enhancement of a DielsÀAlder reaction in water opened doors for future research on solvent effect on the kinetics of a DielsÀAlder reaction. The rate constants of the DielsÀAlder reactions in water are much higher than those noted in organic solvents, establishing the important role of water in realizing organic reactions.7 In addition to obvious economical and environmental advantages, water is known to have surprising beneficial effects on the kinetics of organic reactions.7À12 Studies on solvent effects are generally carried out by means of relationships between reactivity properties that are reaction rate or several types of selectivity and empirical parameters representing different kinds of soluteÀsolvent interactions.13À15 Gajewski proposed an effective correlation between rate constants of four different reactions and cohesive energy densities of solvents and solvation parameters.15 The studies carried out in the recent past have demonstrated that ionic liquids can influence the kinetics of these reactions.16À20 A previous report from this laboratory has demonstrated that rates of intermolecular DielsÀAlder reaction of cyclopentadiene with methyl, ethyl, and butyl acrylates in
r 2011 American Chemical Society

different ionic liquids are slowed down due to high viscosity of ionic liquids,21 since it will be difficult for reactants to interact with each other due to dense solvent environment. However, the role of viscosity in ionic liquids on an intramolecular DielsÀAlder reaction of (E)-1-phenyl-4-[2-(3-methyl-2-butenyloxy)benzylidene]-5-pyrazolone was analyzed using theoretical models to recommend the predominant role of microviscosity rather than of the bulk macroscopic viscosity.22 An earlier report from our group has demonstrated that the addition of cosolvents to ionic liquids brings a dramatic decrease in the viscosity of the solution.23 Since the solvent mixture consisting of an ionic liquid and a cosolvent is less viscous, it may act as effective solvent medium for carrying out organic reactions. The extent of decrease in viscosity of the ionic liquids depends on the nature and amount of the cosolvent added. Further, the polarity of the solvent mixture can also influence the kinetics of organic reactions. In this connection polarity parameters electronic transition energy ETN, hydrogen bond donor ability; acidity R, hydrogen bond acceptor ability; basicity β and polarizabilty π* of pure ionic liquids and ionic liquidÀcosolvent binary mixtures have been investigated.24,25 The nonideality in the polarity parameters in the ionic liquidÀcosolvent mixtures indicated soluteÀsolvent interactions that can influence the rates and selectivities of organic processes in a remarkable manner. In continuation of our ongoing work on ionic liquids,26,27 we now examine the issue of whether newly created solvent media comprising ionic liquids and cosolvent can influence the rates and stereoselective reactions of a popular bimolecular organic reaction, i.e., the DielsÀAlder reaction. The
Received: June 2, 2011 Revised: July 23, 2011 Published: July 28, 2011
10211 | J. Phys. Chem. A 2011, 115, 10211–10217

The progress of the reaction was monitored by following the time-dependent decay of the absorbance peak of 1 at λ = 380 nm. the time dependence of the decay is calculated to give pseudo-first-order rate constants. Phys.29 These authors noted that the slope of relative rates versus relative viscosities for an intramolecular DielsÀAlder reaction was much greater than the one noted during the kinetic study of Claissen rearrangement in these solvents. and a linear increase in the dimerization rate was seen.1021/jp205181e |J.2 mM.28 The ionic liquids were characterized by 1H NMR spectroscopy. Firestone and coworkers have interpreted this behavior in terms of the vibrational activation theory. and 100 μL of 0. The first step included the synthesis of organic cation and the second the addition of anion. The translational mode of a molecule is retarded with increasing viscosity resulting into the shifting of the translational to the vibrational mode.The Journal of Physical Chemistry A Scheme 1 ARTICLE were used to determine the second-order rate constants k2. Fourteen microliters of the stock solution was added to 1 mL of the ionic liquidÀsolvent binary mixture resulting in 0. methanol. 1 ð1 Þ where 1-butyl-pyridinium tetrafluoroborate. high vibrational and low translational energies (favored with increasing viscosity) promote the bond-making.3 cP. The temperature of the cell was controlled using the single cell accessory having an accuracy of (0. Ionic liquids used in the present investigation were synthesized and purified according to the reported procedures. DielsÀAlder reaction between anthracene-9-carbinol (1) and N-ethylmaleimide (2) (Scheme 1) has been studied in different binary mixtures of the pyridinium-based ionic liquids with molecular solvents. In this regime. The above reaction was fastest in water alone when compared to methanol. chloroform. in molecular solvents like water. k0 .022 g quantity of anthracene-9carbinol (1) was dissolved in 5 mL of methanol prior to use to give a 0. [4-MBP][BF4]. Since the concentration of 2 is higher that of 1. 1-butyl-3-methyl-pyridinium tetrafluoroborate. Both the rate increase and fall are seen in the viscosity range observed above. The mixtures of ionic liquids with solvents were prepared on the basis of the volume fraction. the volume fraction of the ionic liquid Vf.21 A similar situation is seen in the present context.8a the comparatively lower the reaction rates in ionic liquids as compared to that in water by Tiwari and Kumar who demonstrated that higher viscosities of ionic liquids were detrimental to the progress of the reaction. Chem. Spectrochem and was distilled prior to its use.1 is volume fraction of solvents. The relative effect of viscosity of the medium in relation to the other soluteÀsolvent interactions in governing the organic reaction has been discussed. All the organic solvents used for preparing binary mixtures with ionic liquids were spectroscopic grade. ’ EXPERIMENTAL SECTION Materials. Pyridine was obtained from M/s. 5. Above 1 cP. 10211–10217 . Deionized water with specific conductance of 0.6. and the resulting kinetic parameters. and chloroform. Twenty-five. the reaction selected by us in the present study was about 450À600 times higher than in any ionic liquids examined here.55 Â 10À6 S cmÀ2 was used for preparing mixtures of ionic liquids. and N-ethyl maleimide were purchased from M/s.112 M stock solution of 2 were then added to the cuvette containing 1 mL of the binary mixture of ionic liquids in solvents to give final concentration 2. Thus.30. Kinetic Measurements. 3-Picolene. unrelated to polarity. 115. the reaction was about 10 times faster in organic solvents than in these ionic liquids. 8.070 g portion of N-ethyl maleimide (2) was dissolved in 5 mL of the methanol to yield a 0.3 mM solution of 1 and equilibrated at the desired temperature for 10À15 min. based on which the nature of the soluteÀsolvent interactions has been discussed. This observation is not yet understood on a molecular level.3 cP before dropping with increasing viscosity above ∼1.32 Accordingly. 11. it is clear that in the lower end of viscosity scale the increase in the rates is sharp with viscosity.30 From the above examples it is clear that rates of different DielsÀAlder reactions vary with the solvent viscosities. [3-MBP][BF4]. The dimerization of cyclopentadiene was also examined with respect to the viscosities of different solvents. viscosity.112 M stock solution of the 2. Anthracene-9carbinol and sodium tetrafluoroborate (NaBF4) were used as obtained. While the rate enhancement of the DielsÀAlder reaction was first noted by Rideout and Breslow. The activation parameters for the reaction 1 + 2 have been determined from temperature-dependent kinetics in the [BP][BF4] + H2O. The 1. Aldrich. the relative freedom of movement of the reactants in the 10212 dx. A 0. defined as the ratio of volume of the ionic liquid to volume of the solution. DielsÀAlder reactions share some common features with the Claissen rearrangement like low solvent dependence. a decline in the reaction rates was observed. For example. A 2011.021 M stock solution. At very high viscosities. The nature of the cosolvent was an important determinant of the soluteÀsolvent interactions. 75. respectively. The ionic liquids were dried under vacuum in order to remove excess water. and water content of the ionic liquids was measured before making solution by a Karl Fischer coulometer and did not exceed 30 ppm for any sample.doi. [BP][BF4]. and other ionic liquids.3 dipolar cycloaddition of diphenyldiazomethane with ethyl phenylpropiolate was found to be enhanced with the rise in viscosity of different solvents to about ∼1 cP. However.2 is Vf . Vf. The role of viscosity on the kinetics of DielsÀAlder reactions was studied by Firestone and Vitale and others. the situation pertains to an encounter-controlled regime. which was selected as a model system. namely.1 °C. 2 ¼ 1 À Vf . as the bond-forming reactions are independent of viscosity in this collision-controlled regime.8. The reaction rates level off at ∼1. the rate enhancement in the low viscosity range cannot be accounted for in terms of current kinetic theory. and 1-butyl-4-methyl-pyridinium tetrafluoroborate. The reported rate constants are an average of at least three kinetic runs on different samples and were reproducible to within (5%. 50. Four values pseudo-first-order rate constants ’ RESULTS AND DISCUSSION The DielsÀAlder reaction of 1 and 2 (Scheme 1) was carried out in the binary mixtures of pyridinium-based ionic liquids. However.28 The ionic liquids were synthesized in two steps.29. 4-picolene.30. A 0.31 From these examples.

This could be accounted for by the fact that the extent of reactivity damping by high friction can be saturated beyond a certain limit. 115. In order to assess the role of viscosity.15 K. ionic liquid. In such a highly viscous environment. The plots of ln k2Àln η for binary mixtures of [BP][BF4] (9). The resulting soluteÀsolvent specificity can overcome the effect of frictional forces in terms of decreasing viscosity. i. a similar preferential interaction between the reactant/the transition state with either of the components of the binary solvent mixtures is certainly plausible. consequently slowing down the reaction. A 2011.2 for binary mixtures of [4-MBP][BF4] (9) and [3-MBP][BF4] (O) in chloroform. [3-MBP][BF4] (b). Chem. and [4-MBP][BF4]) with methanol studied at 298. which are known to have similar polarity ranges. [3-MBP][BF4].e. the uniformity in the trend indicates an absence of any highly specific interactions between the reactants and the components of the binary mixture. Figure 4. It is noteworthy that the sensitivity of the rate constants is greater for the compositions within the lower viscosity range. The remarkable variation can be attributed to the fact that in addition to the viscosity of the medium. Rate constants k2 for the DielsÀAlder reaction 1 and 2 in binary mixtures of all three ionic liquids ([BP][BF4]. 10213 dx.15 K show different behaviors as compared to ionic liquidÀchloroform mixtures (Figure 3). Ionic LiquidÀChloroform Binary Mixtures.2. 10211–10217 .. Figure 3. additional soluteÀsolvent specific interactions seem to play a decisive role in determining the reactivity. the rate constants were also plotted as a function of viscosity (Figure 2). Kinetic measurements were limited to two pyridinium-based ionic liquids. where the increasing concentration of ionic liquids causes a 10-fold increase in viscosity. [3-MBP][BF4] (O). The monotonic decrease confirms the fact that in the ionic liquidÀchloroform system the rate of the reaction is primarily dominated by the viscosity of the reaction medium. microenvironment of the encounter pair become limited. The intermediate polarity of chloroform is apparently compatible with that of the ionic liquids used. Methanol is also capable of forming hydrogen bonding with a wide variety of substrates. For the DielsÀ Alder reaction between 1 and 2. The plots of rate constants k2 vs Vf.15 K. The spatial inhomogeneity resulting from such binary mixtures was manifested as preferential solvation of the spectroscopic polarity probes. The polarity of methanol differs significantly from that of the pyridinium ionic liquids. Phys. The plots of ln k2Àln η in binary mixtures of [3-MBP][BF4] (9) and [4-MBP][BF4] (O) in chloroform at 298. Figure 2. In terms of soluteÀsolvent interactions.doi. Figure 1 shows second-order rate constants k2 for the DielsÀAlder reaction of 1 with 2 in the binary mixtures of pyridinium-based ionic liquids in chloroform as a function of the volume fraction of the second component in the binary mixture. b. reactants cannot see each other. since [BP][BF4] is insoluble in chloroform due polarity difference and forms a biphasic system. The rate constants for the DielsÀAlder reaction in the binary mixtures of ionic liquids in methanol decrease with the addition of ionic liquids to methanol in a sigmoidal form (Figure 4). [3-MBP][BF4] and [4-MBP][BF4]. The plots of rate constants k2 vs volume fraction of ionic liquid. Ionic LiquidÀMethanol Binary Mixtures. it is seen that the rate constants remain at a nearly constant value—a “plateau”—in the intermediate composition range.The Journal of Physical Chemistry A ARTICLE Figure 1. The rate constant k2 decreases with an increase in concentration of ionic liquids in the binary mixture. for binary mixtures of [BP][BF4] (9). a. and [4-MBP][BF4] (2) in methanol 298.25 In the present system. rather than any other soluteÀ solvent interactions. Vf. and [4-MBP][BF4] (4) in methanol.1021/jp205181e |J.

[3-MBP][BF4] (O). The dominant role of the hydrophobic effect is. From the plots of rate constants k2 versus different concentrations of ionic liquids in water shown in Figure 5.82 Â 10À3 MÀ1 sÀ1 for pure water to 2.2 = 0.25 The polarity of mixtures of ionic liquidsÀmethanol and ionic liquidsÀchloroform shows different behavior due to the large polarity difference between methanol and chloroform.doi. Phys. Similarly the rate constants decrease for a binary mixture of [3-MBP][BF4] and [4-MBP][BF4] in water as 24.2 = 0. The corresponding viscosity increases for [3-MBP][BF4]À water mixture from 0. The plots of ln k2Àln η in binary mixtures of [BP][BF4] (9).42 cP and for [4-MBP][BF4]Àwater mixture from 0. 115.2 = 0. in determining the reactivity between 1 and 2.07 Â 10À3 MÀ1 sÀ1 for Vf. The identity of the ionic liquid does not make an appreciable difference in the observed rate constants. A 2011. The observations are indicative of the preferential solvation of the reactant/transition state by the methanol molecules or hydrogen bond donor (HBD)Àhydrogen bond acceptor (HBA) complex formed between ionic liquids and methanol rather than the ionic liquid. The high degree of similarity of rate profiles for the different ionic liquids. This hydrophobicity of water decreases with addition of ionic liquids and solvates the reactants more independently. the polarity alters nonideally and is directed by ionic liquids only.25 But in the case of an ionic liquidsÀ chloroform binary mixture.82 Â 10À3 MÀ1 sÀ1 for pure water to 5. it is possible to throw light on correlating the reaction rates with the concept of pairwise interactions. The decrease in rate constants of DielsÀAlder reaction with addition ionic liquids to water has been ascribed to three factors: (1) decreased polarity of the transition state in ionic liquids. because of the synergetic effect. Figure 6. the viscosity change is very high but rate constant does not show much change as compared to the earlier region. The rate constants in an ionic liquidsÀ methanol system decrease nonideally but in a certain composition range remain invariant.   k2 2 GðCÞm À nΦM1 m ð2Þ ln ¼ 0 RT k2 10214 dx. and [4-MBP][BF4] (2) in water. in addition. A similarity between the rate profiles for the three ionic liquid mixtures is much greater in the presence of water as a cosolvent rather than methanol as the other component. This additivity principle is used to analyze the thermodynamics of soluteÀsolute interactions in aqueous media. The plots of rate constants k2 vs Vf. Following the pioneering contribution of Engberts and his school35 on hydrophobic hydration and its use in explaining DielsÀAlder reactions in highly aqueous solutions. as discussed previously for the binary mixtures of methanol. The difference in the polarity of water and ionic liquid as well as the hydrogen bonding capacity of the water molecule could be the decisive factors. At this stage.35 The linear relationship between ln(k2 /k20) versus molality of cosolvent shows the presence of pairwise interaction and has been incorporated into a quantitative analysis of kinetic medium effects for highly dilute solutions give by eq 2.2 of ionic liquids in water.33 cP.2 of [BP][BF4] ionic liquids and viscosity increases from 0. Chem.82 Â 10À3 MÀ1 sÀ1 for pure water to 2. In the ionic liquidsÀchloroform system. the rate constants decrease from the 24. a reasonable explanation for the dramatic increase in reactivity in the highly aqueous region. other than viscosity. while probably stabilizing the transition state through hydrogen bonding effects.1021/jp205181e |J.01 Â 10À3 MÀ1 sÀ1 for Vf. The viscosity also increases with increase in concentration of ionic liquid in water. respectively. In the highly aqueous region. and [4-MBP][BF4] (2) in water at 298. it is observed that the rate constants decrease with increase in concentration of ionic liquids in water. c.The Journal of Physical Chemistry A ARTICLE Figure 5. it is of interest to invoke the effect of pairwise interactions operating in the system. Beyond this composition. 10211–10217 .34 It is difficult to quantify the extent of the hydrophobic effect for the system under study. The relatively higher proportion of methanol in the solvation shell of the reactants “shields” the reaction from the increasing friction. In the case of a binary mixture of ionic liquidsÀ (2) the antihydrophobic effect of ionic liquids which solvate the organic reactants independently.2 in the binary mixtures of [BP][BF4] (9). nevertheless. trigger points are the significant points where the exponential rates changed more drastically.2 of ionic liquids in water and 24.33 From Figure 5.71 Â 10À3 MÀ1 sÀ1 for Vf. Earlier reports suggest that the kinetics of organic reaction is drastically accelerated in water due to the hydrophobic effect of water.15 K. [3-MBP][BF4] (O). The reactant/transition state does not experience the rising ionic liquid proportion coupled with a concomitant decrease in methanol concentration. Ionic LiquidÀWater Binary Mixtures.89 to 1.40 cP.89 to 1. in which the polarity of mixture is higher than those of the pure solvents. the polarity varies in a synergetic manner. The results suggest the presence of additional factors. the rate constants do not vary polarity.89 to 1. and (3) diminished hydrogen bonding effects of water in the transition state. implying that the methyl substituent is distant from the reaction center in the solvated form of the transition state. which slow down the diffusion process reaction rate. indicates an even greater extent of preferential solvation in aqueous systems as compared to methanol binary systems. Within this framework. the rate effects are discussed in terms of pairwise Gibbs function interaction parameters attributed by the respective interactions of the cosolvent molecules with the initial state and the activated complex of the reaction.

22 kcal molÀ1 for the concentration of [BP][BF4] in water from Vf. The temperature dependent rate constants k2 for the DielsÀAlder reaction in binary mixtures of [BP][BF4] in water are shown in the form of Arrhenius plots (Figure 8). Table 2. The surface tension of pyridinium based ionic liquids shows 44 mN 3 mÀ1.15 0. The G(C) Values for the DielsÀAlder Reaction in the Aqueous Solutions of Ionic Liquids at 298.40 Δ#G. The plots show that the variation in k2 for the DielsÀAlder reaction in different compositions of highly aqueous region of the binary mixtures of [BP][BF4]Àwater. and [4-MBP][BF4] are shown in Table 1.04 (9). The cosolvents stabilize the initial state to a larger extent than the transition state which increases the Gibbs energy of activation leading to a decrease in rate constant.11 (2) and 0.20 0.56 84. The highly negative values of G(C) designate that the initial state is more stabilized by ionic liquids which did not allow any significant aggregation of the diene and dienophile at concentrations used for the kinetic measurements.2 0. A 2011. Δ#H.36 The surface tension of mixture decreased rapidly in dilute solution but almost did not vary in the concentrated solution. k20 is the a rate in pure water.76 81. From a comparison with similar types of reactions.4 Figure 8. [3-MBP][BF4] (O).00 À42.48 35.09 À0.59 85. The activation parameters enthalpy of activation Δ#H.12 À0. one of important properties of ionic liquids is surface tension.17 À0. It has been reported that surface tension of ionic liquids is governed by the anions. It is seen that the enthalpy of activation. Phys.15 (Figure 9).23 When the ionic liquid concentration increases.03 TΔ#S. and [4-MBP][BF4] (2) in highly aqueous media at 298. Temperature Dependent Kinetics of the DielsÀAlder Reaction.30 À55.72 À27.63 83. and G(C) is the difference in Gibbs energy of interaction between the cosolvent and the initial state and the cosolvent and the transition state.13 88.07 (O).40 0. kJ molÀ1 À35.41 60.25 86. 0. and free energy of activation Δ#G were determined for seven different compositions of [BP][BF4] in water.22 51.7 À2629.15 K. possibly due to differences in polarities which led to different interactions with the ions in the ionic liquids.04 to Vf. m is the molality of cosolvent. 1 2 3 4 5 6 7 Vf. Ionic liquids possess a lower surface tension than water and it decreases with the addition of ionic liquids. entropy of activation Δ#S. no. Table 1. kJ molÀ1 82. The result shows the [BF4]À-based ionic liquids are very active at the surfaces. Activation Parameters for the DielsÀAlder Reaction in the Binary Mixtures of Ionic Liquids [BP][BF4] in Water at 298. [3-MBP][BF4].07 0. which shows that the surface tension of the medium is the prevailing important role in kinetics of the DielsÀAlder reaction. respectively. The plots of ln k2À1000/T for Vf. J kg MÀ2 À2010.3 À3031. 10211–10217 . is more dramatic as the surface tension. Chem.09 À49. The presence of a methyl group and position of the substituent on cations of ionic liquids also affect the solvation of diene and dienophile. G(C) represents the overall effect of the cosolvent on the Gibbs energy of activation for the DielsÀAlder reaction and is obtained from the slope of a linear plot of ln (k2/k20) vs molality m of the cosolvent. it appears that the values of G(C) for ionic liquids are much higher than those for organic solvents. The decrease of the viscosity of ionic liquids by the addition of cosolvents followed a different pattern depending on the nature of the cosolvents added.19 À0.2 = 0.29 30. The ionic liquids decrease the surface tension of water which does not lead to cavity formation in water more easily and solvate the reactants.2 = 0.1021/jp205181e |J.63 to 30. S. The G(C) values calculated for aqueous solutions of [BP][BF4]. The surface tension of ionic liquids in aqueous solution decreases with increase in the concentration of ionic liquids.14 À0.03 À34.15 K Δ#H.12 À0. 0.The Journal of Physical Chemistry A ARTICLE Figure 7. Hence in highly aqueous medium the change in rate constants. k2.63 41. n is the number of water molecule involved in activated complex. Φ is the practical osmotic coefficient of water (Φ = 1 for highly aqueous solution).95 À9.11 0. decreases from 47.11 where k2 is second order rate constant for the DielsÀAlder reaction in a binary mixture of ionic liquids in water. In addition to this.15 K ionic liquids [BP][BF4] [3-MBP][BF4] [4-BP][BF4] G(C).60 kJ mol-1 47. The activation parameters for the reaction of 1 with 2 were determined from the temperature dependence of k2 in [BP][BF4]Àwater binary mixtures shown in Table 2. Plots of ln(k2/k20) vs m of [BP][BF4] (9). kJ molÀ1 KÀ1 À0. These values were not in agreement with the qualitative prediction that the 10215 dx.71 91. This remarkable behavior may indicate the presence of other factors responsible for the kinetics of the reaction. the viscosity does not increase a great deal in the dilute solution but increases rapidly in the concentrated solution.04 0. M1 is the molar mass of water.2 (volume fraction of [BP][BF4] in water) = 0.15(3) for the binary mixture of [BP][BF4] in water.71 Δ#S.doi. 115.

beyond these concentrations of ionic liquids. e.37À39 However. The results point toward the possibilities of manipulating the reactivity of organic compounds by a judicious and well-informed choice of ionic liquid binary systems. hydrophobic interactions will become entropically slightly more favorable. aqueous salts solutions.acs. 1 and 2 will become more and more preferentially solvated by the ionic liquids. In aqueous systems.The Journal of Physical Chemistry A ARTICLE Figure 9. The unfavorable Gibbs free energy for solution in water is the result of strongly negative entropy of solution which prevails over the favorable enthalpic contribution. water gradually loses its typically aqueous character. 2.res. the entropy of activation exhibits an equally dramatic decrease. additional soluteÀsolvent interactions dominate the kinetic profile depending on the property of the cosolvent used. and nonaqueous salt solutions with the help of solvent cohesive pressure or CED of solvent systems and the activation volume of the DielsÀAlder reactions. the effect of viscosity is a consistently effective feature for all the ionic liquid systems The reactivity in chloroformÀionic liquid binary mixtures is closely related to the viscosity of the reaction medium. i. where the concentration fluctuations are at their maximum. 115. the binary mixtures start to behave like a common solvent. despite the strong intermolecular forces. It is hoped that the above study will open doors for solvent engineering via the use of physicochemical property. The term hydrophobic hydration refers to the interactions of apolar solutes and At composition in the highly aqueous region. Figure 10. 3. The plots of activation parameters (Δ#Y) Δ#H (9). The domination of entropy effects is often found for chemical processes in water and in water-rich solutions. Several years ago. ’ ASSOCIATED CONTENT S b Supporting Information.46 The nonavailability of physicochemical data on the ionic liquids solutions restricts our explanation on the above basis. a more complex correlation is observed wherein the role of viscosity cannot be completely discounted. how an apolar solute affects the water structure in its immediate environment. The kinetic data can be interpreted in terms of a pairwise model built upon enforced hydrophobic hydration. reactants will have to overcome a “higher barrier” in a more viscous medium.e. 10216 dx.45 It is found that the association process is entropy driven. leading to a decrease in the rate of the reaction. water becomes even more structured by the formation of hydrophobic hydration shells as seen by numerous spectroscopic studies.15 are spectacular. The changes of Δ#H and TΔ#S across the mole fraction range of 0 < x2 < 0. Phys. The reaction is slowed down by addition of structure-promoting cosolvents..44. indicating the dominance of the frictional forces.15 K for the reaction of 1 with 2 on the mole fraction of [BP][BF4] in dilute aqueous solutions is dramatic. The effects almost fully compensate each other. ’ AUTHOR INFORMATION Corresponding Author *E-mail: a.1021/jp205181e |J. and Δ#G (2) for the binary mixtures of [BP][BF4]Àwater. 10211–10217 . 4. As a result. A high degree of preferential solvation is certainly responsible for the deviations from ideality observed. It has been also observed that the entropy of activation might play an important role in the organic reaction which leads to a phenomenon known as entropyÀenthalpy compensation. units are in kJ molÀ1. The activation parameters for the aqueous binary mixtures showed enthalpyÀentropy compensation effects.37À40 The dependence of Δ#H and TΔ#S at 298. Finally. The enthalpy of activation decreases upon addition of [BP][BF4]. At a critical concentration of water molecules. leading to smooth changes in rate and activation parameters upon variation of the ionic liquids composition. For the methanol and water binary mixtures. This material is available free of charge via the Internet at http://pubs. the standard enthalpy of the solution process is usually small and favorable whereas the entropy change is large and negative. A 2011. the presence of hydrophobic forces is observed distinctly. and the driving force for the dramatic rate effect in water will be lost. viscosity of the solvent medium.41À43 Hence in the water-rich media the free energy of activation for the DielsÀAlder process is only moderately affected by the addition of ionic liquids to The plot of enthalpyÀentropy compensation for the DielsÀAlder reaction of 1 and 2 in [BP][BF4]Àwater binary mixture is shown in Figure 10. Most importantly.. ’ CONCLUSIONS The above results show the following: 1. ÀT4#S (O). Illustration of enthalpyÀentropy compensation plots of Δ#HÀΔ#S for the DielsÀAlder reaction of 1 and 2. Introduction of an apolar solute into aqueous solution is characterized by an unfavorable change in standard Gibbs energy at room temperature. Chem. one of us had demonstrated an alternate explanation of the rate enhancement in DielsÀAlder reactions in water. However. Simultaneously. Three tables containing the values of second-order rate constants.

. 449. (b) Sternbach. Org. K. E. M. and Opportunities. C. J. D.. 2001. (46) (a) Kumar. Chem. 230. (24) Khupse. I. M. Soc. Ed.. (d) Kumar. J. 30. J.-J. Chem. Sethi. M. American Chemical Society: Washington. B 1997. 38. 1991. J. (b) Harifi-Mood. Vitale. Kumar.. Am. Best. J. J. 69. 72. Chem. W. 2006. L. 468.. Sarma. (e) Hallett. N.. (18) Jaeger. B. 654. J. Chem. Chem. E. Mrksich. Angew. Org. T. Chem. Chem. Chem. M. A. A. (b) Gholami.. Am. A. B. 2004. Ed. 104. J. J. J. J. 1992.. 2653. A.. F. T. A. 68. 208. J. Tetrahedron Lett. J. In Ionic Liquids IIIB: Fundamentals. S. 4241. K. (39) Besseling. 1994. W. 1312.. 61. C. Angew. (16) Kumar. M. C. N. Engberts. 24. (31) Coster. Rev. R. Scherrmann. R. 4. 4241. Perkin Trans. Phys.. 2803. A. B. C. G.. 113. 2008. N. W. A. 113.. 2003. J. J. C. Keim.. (b) Blokzijl. S. 18. W. 1987. 4612. N. Mayoral. C. J. N. A.. J. (e) Lubineau. A. Engberts. 124. M. F.. 2007. J. Int. A.. Tetrahedron Lett. Commun.. Blandamer. Soc. Jr. H. 68. Engberts. C 2010. New Delhi for an award of a Senior Research Fellowship. Chem. M. (b) Lubineau. J. Kumar. P. J. L. J. Espel. (30) Swiss. Tetrahedron Lett. 1998. Bond. J. Engberts.. Tetrahedron Lett. Org. A. 2002. 113. G. Gholami. B. A. Chem. (38) Lee. Acc. 1986. (d) Lubineau. A. M. 115. Int. (b) Breslow.. G. 517. Recent Applications of Chloroaluminate Ionic Liquids in Promoting Organic Reactions. Phys. M... Y. 2011. 1993. J. M. Chem. A. Chem. 1785. F. J. Chem. Seddon.. H. 4248. 21775. A. 1982. Chem. Org. C. (33) Butler. Synthesis 1994. Data 2009. A. (b) Kumar. J. 1989... C.. Streefland. J. 279. S.. 109. T. Welton. (7) Reichardt. 2071. Pure Appl. DC.. 1975. 93.. 99. G. Chem. R.. 3508.(b) Wasserscheid. thanks CSIR. 376. 126.. Rossana. Chem. Inorg. H. J. A.. F. J. G. Am.. B. W. 126. W. F. Salminen. B. D. M. A. S. M. Mol. A. N. R. ’ REFERENCES (1) (a) Welton.(c) Kumar. T.. P. (11) Grieco.. Chan. Soc. J. L. I. (40) Blokzijl. Chem. Rev. Soc.. 2003. Ionic Liquids in Synthesis. Chem. N. Y. Talebi. Int. Soc. Phys. Chem. 9075.. 2002.1021/jp205181e |J. 21. Queneau. 2002. Am. Mainar. 23. J. 8111. N. Chem. 55. Y... 2000.. Org. 1980. J. N. Angew... W... Hoekstra. 1996. (c) Torriero. N. R. N. J. D. 806. R. Meindersma. 9. ACS Symposium Series 818. 11222. A. 303. 2000. J. F. A. 2003. 496. Chem. 32. Soc.D. J. J. D. 159. M. (e) Blokzijl. Soc. A. Am. Chem. J. Chem. Chem. 1037. G. Challenges. Rev. Seddon. 114. 114.K. 10217 dx. (b) Kumar.. J.. 5440. (3) (a) Lane. Pieracinni. 1999. Transformations and Processes. Kumar. Chem. S. 1996. 485. J.. 113. 1994.. Water. (10) Cativiela. 2004. 5369.. B. 1996. Khalili. M. 47.. 108. M. Baker. Queneau. R. R. J. (15) Gajewski. Tetrahedron Lett.. Cunningham. 52.. A. Chem. D.doi. Chem. Ber. A. de Haan. F. 2 1997. Org.. 1994. C. 4. J. Welton. M. K.. 45. N. (19) Earle. 1713. H. Seabury. R. Chromatogr. J.. K. A.. B.(b) Rogers. Chem. A.. 26. Pawar. J. D.. 140. M. Kumar. P. (e) Valgimigli. S. 1545. Firestone. Ed. 1991. Y.. P. J. L. B. W. Chem. 1982. Soc. 1981. A: Chem. J... 7947. Solution Chem. N. D. Chem. McCleskeya. Graltzel. Dunlop. New Delhi for a JC Bose National Fellowship ((SR/ S2/JCB-26/2009) to him. R. Soc. J. S. P. A. L. 5411. Y. T.. (e) Kumar. 2004. 33. 59. K. 1979.. F. Liotta. 1968. Org. Chem. 102. MacFarlane. Pfeil. Blandamer. Y. 72. Habibi-Yangjeh. 118.. M.. B. 45. Org. J. R. Int. Engberts. Blackie: London. Liq. Am. Soc. Gil. Swiss. R. N. 12. (28) (a) Papaiconomou. Green Chem. Baker. J. Org. J. A.. Habibi-Yangjeh. 1985. Siriwardana. Int. Phys. 112.. J. 143. D. Phys. 113. Tucker. 2005. A. Hollenkamp. Tetrahedron 1989. C. J. Pawar. Pawar. Tetrahedron Lett. 2005.. Engberts. A 2004. J. (12) Li. Queneau. Chem. 59. 209. (e) Chiappe. P. Breslow. Martınez.. Org. D.. Chem. Org. Lusztyk. F. A. (b) Sanchez. Lancaster. 1988. R. C. Forsyth. R. Res. (b) Forsyth. Lett. Lyklema. J. Burgess. Queneau. Progress. Wang. J. 2023. (c) Burrell. Chem.. R. Burke. 1168. 26. T. W. B 2009. (c) Poole. A. A. G. R.. Data 2006. R. (b) Bonhote.. 44. Clare. Deacon. J. Eng. Phys.. 51.. (d) Dolbier. 1990. The authors appreciate the anonymous reviewers for offering constructive evaluation of the work. M. A 2002. (25) Khupse. A. Zhang. 13. Salvatella.. 5163. R. Garcıa. 11923. Sesto. Chem. 1991. W. 7604. 2000.K.J.. J.. Coyne. H. 7681. R. S. Seddon. J. 2006. Eng. Engberts. 1197. A. Am. Chem. 32. R. W. R. Graziano. 29. Phys. R. L.. Soc. 40. 1980. Burke. Org. 46. M. N.. J. Am. D. A. S. N. M.. Chem. F.. J. Blandamer. Bienayme.. (22) Tiwari. 711. Chem. A. Wiley-VCH: Weinheim. Plenum Press: New York. Org. Chem.. J. 6411. Franks.The Journal of Physical Chemistry A ARTICLE ’ ACKNOWLEDGMENT N. N. J. K.. Bayley. Phys.. J. thanks Department of Science and Technology. Am. J. Catal.—Eur.. J. (29) (a) Firestone. B. Mol. A. 73. Soc. J. p 350. M.. Phys... Organic Reactions in Aqueous Media.. R. ACS Symposium Series 902. (42) Kwon. 2010. 389. Jager... 101. 1991. McCormac. 11923.. 589. J. Chem... F. R. S. 115. S. Deshpande. Cheng. 111. J. U.. (6) Sauer. A. M. Soc. Ed. 741. 4393. Angew. A 1999. DC. E. A. (26) Rai. J. 779. (8) (a) Rideout.. N. 275. Org.. M. 2008. American Chemical Society: Washington. 1610. 2008. Chem. 3772. J. A. Soc. Organic Synthesis in Water. Dias. F. (43) Blokzijl.. M. (d) Earle. 10211–10217 . (20) Lee. H. Soc.. (2) (a) Wasserscheid. 1. (35) (a) Hol. Wiley: Chichester. 5500. R. Chem.. (f) Weingartner. Khupse. Kumar.. L. N. 106. 35. J. Ed. Ingold.. 57. 4824.. Germany. R. A. J. 2160. H. J. Pentaleri. Mayoral. 23. Chem. 1987. 19. Pringle. (27) (a) Kumar.. 1996. 1999.. Am. L.. Chem. (34) Butler.. (5) (a) Lubineau. M. B. Auge. Am. 1419... M. Rev. K. Blandamer. J. A. Angew. S. (14) Cativiela. F. 2007. 54. L. B. (4) MacFarlane. A. A. B 2011. 39. Rogers. Coyne. Burgar. Bergman. (41) Blokzijl. Yu. Sustmann. 1979. Chem. A. Tetrahedron Lett. (45) Blandamer.. D. (17) (a) Aggarwal. Phys. B. Queneau. Welton. R. K. F. A.. 3745. J. B. Blandamer.. Y. Chem. Papageorgiou. New J. A 2011. M. (f) Lubineau. Solvent Effects in Organic Chemistry. J. (c) Lubineau. N.. 2008. I... 1985.. Ed. A. J. (32) Firestone. J. (f) Pirrung. Ed. Phys. (9) Li. A.. D. J. Seddon... 1001. P. 2004. Int. D. Pawar. 2 1997. P. Prausnitz... A. 1391. J. N. Urieta. M.. Angew. S. Chem. Chem. (c) Dumas. Soc. Garcıa. Aust. 2399. (13) (a) Gholami. Cunningham. I. W. R. 7816. G. A Comprehensive Treatise. W. Chem. 57. 6691. 69.. A.. Ionic Liquids: Industrial Applications to Green Chemistry. Chem. M. (37) Abraham. Onink. Salvatella. J. J. (23) Khupse.. J. Chem. (36) (a) Liu. Kalyanasundaram. 23. M. Chem. 653. (d) Blokzijl. Am. (44) Engberts. J. S. Eds. Rev. 2004. Perkin Trans.. M... Chem. R... Malleron. 1999. Chem. 2461. Phys. J. D. 2085. 101. Chem.. A. N. Verlag Chemie: Weinheim. Chem. Green Chem. J. B 2010. 18. Yakelis. 2009. 1419. F.. M. A.. D. Chem. R. J. 1997. (21) Tiwari. Kumar. S. 2004.. Soc. MacFarlane. 1993. A. 49. 103. Engberts. J. D. A. 1993. Chem. D. J. (c) Blokzijl. Chem. T. C.. 6909... 783. Green Chem. Abraham.