Investigations on substituent and solvent effects on solvolysis reactions Part IX. The influence of polar substituents on the imidazole catalyzed hydrolysis of 2,4-dinitrophenyl acetates in water

Abstract

The imidazole catalyzed hydrolysis of polar substituted 2,4-dinitrophenyl acetates in water has been investigated at different temperatures. The observed rates correspond to the bimolecular nucleophilic addition of the imidazole at the carboxylic carbon atom followed by a very fast hydrolysis of the N-acetylimidazole in water. The influence of polar substituents in the acid moiety of the ester molecule on the hydrolysis reaction can be described by an electrostatic dipole–dipole interaction in the same way as the neutral hydrolysis of polar substituted ethyl acetates.

References

1. G. Schmeer, C. Six and J. Steinkirchner, J. Solution Chem., 1999, 28, 211.
2. E. K. Euranto, Ann. Acad. Sci. Fenn., A 2, 1970, 152, 1.
3. J. F. Kirsch and W. P. Jencks, J. Am. Chem. Soc., 1964, 86, 837.
4. G. Schmeer and J. Barthel, Z. Phys. Chem. N.F., 1984, 140, 17.
5. D. E. Schmidt and F. H. Westheimer, Biochemistry, 1971, 10, 1249.
6. D. B. Olsen, T. W. Hepburn, S. Lee, B. M. Martin, P. S. Mariano and D. Dunaway-Mariano, Arch. Biochem. Biophys., 1992, 296, 144.
7. V. V. Katyshkina and M. Y. Kraft, J. Gen. Chem. USSR, 1959, 29, 65.
8. M. L. Bender and B. W. Turnquest, J. Am. Chem. Soc., 1957, 79, 1656.
9. W. P. Jencks and M. Gilchrist, J. Am. Chem. Soc., 1968, 90, 2622.
10. K. Köhler, R. Skora and E. H. Cordes, J. Am. Chem. Soc., 1966, 88, 3577.
11. A. D. Mitchell, L. C. Cross and L. E. Sutton, in Table of Interatomic Distances and Configuration in Molecules and Ions, Chemical Society, London, Specialist Publ. No. 11, 1958, pp. 1.
12. O. Exner, in Dipole Moments in Organic Chemistry, Georg Thieme Verlag, Stuttgart, 1975.
13. B. M. Craven, R. K. McMullan, J. D. Bell and H. C. Freeman, Acta Crystallogr. Sect. B, 33, 2585.
14. R. D. Brown and B. A. W. Coller, Theor. Chim. Acta, 1967, 7, 259.
15. P. W. Atkins, in Physical Chemistry, Oxford University Press, Oxford, 1990.
16. G. Schmeer and P. Sturm, Phys. Chem. Chem. Phys., 1999, 1, 1025.