Reactions of Carbonyl Compounds in Basic Solutions. Part 30.¹ The Effect of 2-Formyl, 2,6-Diformyl and 2-Trifluoroacetyl Substituents on the Alkaline and Neutral Hydrolysis of Methyl Benzoate and Phenyl Acetate

Abstract

Rate coefficients are measured for the alkaline hydrolysis of methyl 2-formyl-, 2,6-diformyl- and 2-trifluoroacetyl-benzoates and for the alkaline and neutral hydrolysis of 2-formyl-, 2,6-diformyl-4-methyl- and 2-trifluoroacetyl-phenyl acetates in water at several temperatures: the relative rates of hydrolysis and activation parameters demonstrate neighbouring group participation by the acyl-carbonyl groups in the ester hydrolysis.

References

1. Part 29, K. Agnihotri and K. Bowden, J. Chem. Res., 1997, (S) 308; (M) 1929.
2. A. A. Sinkula and S. H. Yalkowaky, J. Pharm. Sci., 1975, 64, 181.
3. H. Bundgaard, in Design of Prodrugs, ed. H. Bundgaard, Elsevier, Amsterdam, 1985, ch. 1.
4. (a) K. Bowden, Adv. Phys. Org. Chem., 1993, 28, 171; (b) K. Bowden, Chem. Soc. Rev., 1995, 25, 431.
5. K. Bowden and F. P. Malik, J. Chem. Soc., Perkin Trans. 2, 1992, 5; 1993, 7.
6. M. L. Bender, J. A. Reinstein, M. S. Silver and R. Mikulak, J. Am. Chem. Soc., 1965, 87, 4545.
7. K. Bowden and G. R. Taylor, J. Chem. Soc. B, 1971, 149.
8. J. A. Walder, R. S. Johnson and I. M. Klotz, J. Am. Chem. Soc., 1978, 100, 5156.
9. K. Bowden and R. J. Ranson, unpublished results.
10. N. B. Chapman, J. Shorter and J. H. P. Utley, J. Chem. Soc., 1963, 1291; Y. Iskander, R. Tewfik and S. Wasif, J. Chem. Soc. B, 1966, 424; M. Hojo, M. Utaka and Z. Yoshida, Tetrahedron Lett., 1966, 19, 25.
11. T. Nishioka, T. Fujita, K. Kitamura and M. Nakajima, J. Org. Chem., 1975, 40, 2520.
12. C. D. Johnson, The Hammett Equation, Cambridge University Press, Cambridge, 1973.
13. V. Gold, D. G. Oakenfull and T. Riley, J. Chem. Soc. B, 1968, 515.
14. C. Hansch, A. Leo and D. Hoekman, Explaining QSAR Hydrophobic, Electronic and Steric Constants, American Chemical Society, Washington, 1995.
15. A. J. Kirby, in Comprehensive Chemical Kinetics, ed. C. H. Bamford and C. F. H. Tipper, Elsevier, Amsterdam, 1972, vol. 10, ch. 2.
16. J. E. Francis, K. J. Doebel, P. M. Schutte, E. C. Savarese, S. E. Hopkins and E. F. Bachmann, Can. J. Chem., 1979, 57, 3320.
17. Y. Hu and H. Hu, Synthesis, 1991, 325.
18. U. D. G. Prabu, K. C. Eapen and C. Tamborski, J. Org. Chem., 1984, 49, 2792.
19. S. Matsumoto, H. Kobayashi and K. Veno, Bull. Chem. Soc. Jpn., 1969, 42, 960.
20. J. A. S. Cavaleiro, M. de F. P. N. Condesso, M. M. Olmstead, D. E. Oran, K. M. Snow and K. M. Smith, J. Org. Chem., 1988, 53, 5847.
21. D. S. Kemp and F. Vellacio, J. Org. Chem., 1975, 40, 3003.
22. K. Bowden and A. M. Last, J. Chem. Soc., Perkin Trans. 2, 1973, 345.