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IJCB 44B(6) 1283-1287.Pdf Indian Journal of Chemistry Vol. 44B, June 2005, pp. 1283-1287 Hydroxylic solvent effects on the reaction rates of diazodiphenylmethane with 2-substituted cyclohex-1-enylcarboxylic and 2-substituted benzoic acids: Part II Gordana S Ušćumlić*, Jasmina B Nikolić* & Vera V Krstić* Department of Organic Chemistry, Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, P.O. Box. 3503, YU-11000 Belgrade, Serbia & Montenegro E-mail: [email protected] Received 20 April 2004; accepted (revised) 12 October 2004 The rate constants for the reaction of diazodiphenylmethane with 2-substituted cyclohex-1-enylcarboxylic acids, determined in butan-1-ol, 2-methylpropan-1-ol and ethylene glycol, together with the rate constants determined previously in methanol, ethanol, propan-1-ol and propan-2-ol, are correlated using the total solvatochromic equation, of the form log k ∗ = A ο + sπ + aα + bβ, the two parameter model log k = Ao+ sπ* + aα and the single parameter model log k = ∗ Ao + bβ, where π , β and α represent the solvent dipolarity/polarizability, solvent hydrogen bond acceptor basicity and hydrogen bond donor acidity, respectively. The correlation of the kinetic data are carried out by means of multiple linear regression analysis and solvent effects on the reaction rates have been analysed in terms of initial state and transition state contributions. The results obtained for 2-substituted cyclohex-1-enylcarboxylic acids are compared with the results for 2-subsituted benzoic acids under the same experimental conditions. IPC: Int.Cl.7 C 07 C 63/00 Earlier work1-4 showed that in the reaction between γ-hydrogen atoms in the alcohol). The favourable carboxylic acids and diazodiphenylmethane (ddm) in influence of the dielectric constant was expected for the alcohols, the rate-determining step involves a proton reaction in which the route from the initial to the transfer from the carboxylic acid to ddm to form a transition state involves charge separation, but the diphenylmethanediazonium-carboxylate ion pair. stepwise regression showed that the σ∗ term is more Subsequent fast product-governing stages have been important. This indicated the dominant role of the variously formulated5-7. The diphenylmethanediazo- solvating properties of the alcohol, i. e. Lewis bacisity nium-carboxylate ion pair seems most likely to or acidity of the solvent. collapse to give an ester or react with the solvent to In a recent paper9, the hydroxylic solvent effects are give an ether. examined on the reaction of cycloalkylcarboxylic and 1,8 In our previous work , the reactivity of 2- cycloalkenylcarboxylic acids with ddm by Linear substituted cyclohex-1-enylcarboxylic acids with DDM Solvation Energy Realtionships (lser) method. The in various alcohols was examined and the kinetic data correlation equations obtained by stepwise regression for these acids were correlated using the simple and for all the examined acids showed that the best extended Hammet equation. The results have shown approach which helps to understand hydroxylic solvent that the linear free energy realtionships are applicable effects in the reaction lies in the separate correlations of to kinetic data for the 2-substituted cyclohex-1- the kinetic data with the hydrogen bond donating (hbd) enylcarboxylic acid system. Comparisons were made and hydrogen bond accepting (hba) ability of a solvent. with corresponding 2-subsitututed benzoic acid system. For the first time, hydroxylic solvent effects on the The solvent effects on the reactivity of cyclohex-1- reaction rates of carboxylic acids and ddm have been enylcarboxylic acids are proportional to their influence analysed in terms of the initial state and the transition on benzoic acids. It was also concluded that the solvent state contributions. effect is best described through multiple regression of In the present work, we have extended our study9,10 log k vs f (ε) [the Kirkwood function of dielectric of the hydroxylic solvent effects on the reaction of constant (ε−1)/(2ε+1)], σ∗ (the Taft polar constant for carboxylic acids with ddm by means of the lser 11 the alkyl group of the alcohol) and nγH (the number of concept developed by Kamlet et al . 1284 INDIAN J. CHEM., SEC B, JUNE 2005 The second order rate constants for the reaction of The correlation analysis of the log k for all the 2-substituted cyclohex-1-enylcarboxylic acids1,8 examined acids with the solvent parametres π*, α and 12 (system 1) and 2-substituted benzoic acids (system β in protic solvents, showed that there were no 2) were correlated using total solvatochromic satisfactory results. For each examined acid the same equation of the form: problem occurred ⎯ coefficient related to hba log k = A + sπ* + aα + bβ …(1) parameter (b) had a standard error overcoming its o value and making the equation unreliable. As the where π*, α and β are solvatochromic coefficients solvent effect on the examined reaction could not be and Ao is the regression values of the solute property clearly presented when all the solvent properties are in the reference solvent, cyclohexane. taken together, the attempt was made to separate them According to strucutral analogy between the into those that stabilize the transition state and the systems 1 and 2 it seemed of interest to compare ground state. Taking into consideration the reaction obtained results for these acids with identical mechanism (Figure 1) it can be noticed that because substituents. of the charge separation in the transition state solvents of high polarity can stabilize it, making the reaction COOH COOH faster. The similar effect can be produced by the electrophylic ability of the solvent, affecting the carboxylic anion which exists in the transition state. X X On the contrary, the nucleophylic solvating ability can 1 2 be prominent in the ground state, stabilizing the X = H, CH , C H , Cl, Br, I carboxylic proton and slowing down the reaction. 3 2 5 Further examination, using two- and one- Results and Discussion parameter equations with parameters π*, α (effects supporting the transition state) and β (dominating in Values of second-order rate constants for the the ground state) showed more convincing results reaction of 2-substituted cyclohex-1-enylcarboxylic (Tables II and III), using the following forms: acids with ddm, determined in this work at 30oC in butan-1-ol, 2-methyl-propan-2-ol and ethylene glycol, log k = A o + sπ* + aα ...(2) are given in Table I. The reaction rate constants log k = A + bβ ...(3) presented in Table I together with the rate constants o determined previously12 for the reaction of 2-subsituted From the results presented in Tables II and III it cyclohex-1-enylcarboxylic acids1,8 and 2-subsituted can be concluded that the protic solvents influence the benzoic acids12 with ddm in various alcohols were carboxylic acid – ddm reaction by two opposite correlated with the solvent properties, using the total effects. The opposite signs of the electrophylic and solvatochromic equation (1). The solvent parameters nucleophylic parameters are in accordance with the are available for only seven solvents for which they are described mechanism (Figure 1). The positive signs determined by Kamlet et al.13 of the s and a parameters prove that the classical solvation and hbd effects dominate the transition Table I ⎯ Rate constants (dm3mol-1min-1) for the reaction of state and increase the reaction rate, and the negative 2-substituted cyclohex-1-enylcarboxylic acids with o sign of the b parameter points out that hba effects (β) diazodiphenylmethane at 30 C in various alcohols stabilise the initial state before the reaction starts and Substituent Butan- 2-Methyl- Ethylene are responsible for a decrease of the reaction rate. It 1-ol propan-2-ol glycol can be noticed that the equation including the proton- acceptor (β) parameter has lower values of correlation Ha 0.480 0.220 1.962 coefficient (r), from which can be concluded that it is CH 0.238 0.042 1.631 3 a less realiable of the two possible models. C2H5 0.308 0.125 1.583 From Table II it could be seen that the classical Cl 1.307 0.597 5.440 solvation and proton-donor solvent effects are more Br 1.438 0.726 4.984 pronounced for the 2-substituted benzoic acids, than I 1.650 0.853 5.480 for 2-substituted cyclohex-1-enylcarboxylic acids. aRef. 9 The explanation of the fact probably lies in the UŠĆUMLIĆ et al.: HYDROXYLIC SOLVENT EFFECTS ON THE REACTION OF CARBOXYLIC ACIDS WITH DDM 1285 Table II ⎯ Results of correlation of log k for 2-substituted cyclohex-1-enylcarboxylic1,8 and 2-substituted benzoic acids12 with equation (2) a a b c Acid Ao s a Rsd Cyclohex-1-enylcarboxylic -1.92 1.05±0.23 1.30±0.52 0.977 0.08 2-CH3- Cyclohex-1-enylcarboxylic -4.33 1.18±0.43 3.83±0.98 0.971 0.15 2-C2H5- Cyclohex-1-enylcarboxylic -2.39 1.44±0.30 1.41±0.60 0.980 0.08 2-Cl- Cyclohex-1-enylcarboxylic -1.48 1.28±0.29 1.15±0.57 0.976 0.08 2-Br- Cyclohex-1-enylcarboxylic -1.25 1.11±0.25 1.03±0.48 0.976 0.07 2-I- Cyclohex-1-enylcarboxylic -1.14 1.07±0.23 0.98±0.47 0.937 0.09 Benzoic -2.87 0.83±0.36 3.02±0.73 0.975 0.10 2-CH3- Benzoic -4.25 1.57±0.67 4.09±1.32 0.966 0.18 2-C2H5- Benzoic -2.59 1.66±0.33 2.21±0.65 0.985 0.09 2-Cl- Benzoic -1.85 1.93±0.38 1.96±0.76 0.982 0.11 2-Br- Benzoic -1.53 1.48±0.32 1.96±0.64 0.982 0.09 2-I- Benzoic -1.83 1.67±0.31 2.21±0.61 0.987 0.09 acalculated solvatochromic coefficients, bcorrelation coefficient, cstandard deviation of the estimate Table III – Results of correlation of log k for 2-substituted cyclohex-1-enylcarboxylic1,8 and 2-substituted benzoic
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