Abstract
The hydrolysis of β-propiolactone and β-butyrolactone in binary water + dioxane mixtures was investigated by kinetic studies. The following conclusions were reached: First, β-propiolactone is more reactive than β-butyrolactone across the range of water + dioxane compositions. This observation was rationalized in terms of the electric charge flow caused by the β-butyrolactone’s methyl substituent. Second, hydrolysis of these lactones is essentially enthalpy controlled. Third, an increase in the dioxane percentage, which relaxes the intermolecular hydrogen bonds in the ordered structure of water, reduces the enthalpy of activation ΔH # and simultaneously increases the entropy of activation ΔS #(absolute value) for solvent compositions up to 60% dioxane. Fourth, plotting ΔH #/ΔS # against the solvent composition yields an N-shaped curve. This results is a consequence of the quadratic and cubic terms appearing in the expressions of ΔH # and ΔS # as functions of the solvent media composition. Fifth, an ABC classification was set up to characterize the behavior of ΔH #/ΔS # for the solvolysis of these lactones.
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García-Santos, M.P., Calle, E., Casado, J.: Amino acid nitrosation products as alkylating agents. J. Am. Chem. Soc. 123, 7506–7510 (2001)
García-Santos, M.P., González-Mancebo, S., Hernández-Benito, J., Calle, E., Casado, J.: Reactivity of amino acids in nitrosation reactions and its relation to the alkylating potential of their products. J. Am. Chem. Soc. 124, 2177–2182 (2002)
García-Santos, M.P., Calle, E., Casado, J.: A method for the kinetic study of amino acid nitrosation reactions. Polyhedron 22, 1059–1066 (2003)
Lawley, P.D.: Carcinogenesis by alkylating agents. In: Searle, C.E. (ed.) Chemical Carcinogens, Chap. 7, 2nd edn. ACS Monograph, vol. 182. American Chemical Society, Washington (1984)
Pérez-Prior, M.T., Manso, J.A., García-Santos, M.P., Calle, E., Casado, J.: Reactivity of lactones and GHB formation. J. Org. Chem. 70, 420–426 (2005)
Manso, J.A., Pérez-Prior, M.T., García-Santos, M.P., Calle, E., Casado, J.: A kinetic approach to the alkylating potential of carcinogenic lactones. Chem. Res. Toxicol. 18, 1161–1166 (2005)
CRC Handbook of Chemistry and Physics, 85th edn. CRC Press, Boca Raton (2004–2005)
Van Duuren, B.L.: Carcinogenic epoxides, lactones, and halo-ethers and their mode of action. Ann. N.Y. Acad. Sci. 163, 633–651 (1969)
Tommila, E.: The influence of the solvent on reaction velocity XII. The solvolysis of alkyl benzenesulphonates in acetone-water and dioxane-water mixtures. Acta Chem. Scand. 9, 975–988 (1951)
Leffler, E., Grunwald, E.: Rates and Equilibria of Organic Reactions as Treated by Statistical, Thermodynamic, and Extrathermodynamic Methods. Dover, New York (1963), pp. 397–402
Winstein, S., Fainberg, A.H.: Correlation of solvolysis rates. IV. Solvent effects on enthalpy and entropy of activation for solvolysis of t-butyl chloride. J. Am. Chem. Soc. 79, 5937–5950 (1957)
Tommila, E., Jutila, J.: Hydrolysis and alcoholysis of sulphonic esters. Acta Chem. Scand. 6, 844–853 (1952)
Tommila, E., Merikallio, E.: Effect of the solvent on reaction velocity. (VI) Hydrolysis of alkyl esters of benzenesulfonic acid in dioxane-water mixtures. Suom. Kemistil. 26B, 79–80 (1953)
Tommila, E., Tiilikainen, M., Voipio, A.: Effect of the solvent on reaction velocity. (X) Solvolysis of alkyl halides in acetone-water mixtures. Ann. Acad. Sci. Fenn. 65, 1–26 (1955)
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Manso, J.A., Pérez-Prior, M.T., del Pilar García-Santos, M. et al. Solvent Effects on the Enthalpy and Entropy of Activation for the Hydrolysis of β-Lactones. J Solution Chem 37, 451–457 (2008). https://doi.org/10.1007/s10953-008-9250-x
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DOI: https://doi.org/10.1007/s10953-008-9250-x