View PDF Version
 
DOI: 10.1039/A708422F (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 2, 1998, 1483-1488

Kinetics and mechanism of the hydrolysis of tetrahydro-2-furyl and tetrahydropyran-2-yl alkanoates

(Note: The full text of this document is currently only available in the PDF Version )

C. Dennis Hall and Vu Truong Le

Abstract

The kinetics and mechanism of the hydrolysis of tetrahydro-2-furyl and tetrahydropyran-2-yl alkanoates in water and water–20% ethanol are reported. In acidic and neutral media, kinetics, activation parameters, 18O isotope exchange studies, substituent effects, solvent effects and the lack of buffer catalysis point clearly to an AA1-1 mechanism with formation of the tetrahydro-2-furyl or tetrahydropyran-2-yl carbonium ion as the rate-limiting step. There is no evidence of a base-promoted BAC-2 mechanism up to pH 12.

References

  1. B. Capon, Chem. Rev., 1969, 69, 407 CrossRef CAS.
  2. T. H. Fife, Adv. Phys. Org. Chem., 1975, 11, 108.
  3. R. A. McClelland, Can. J. Chem., 1975, 53, 2763 CAS.
  4. P. Salomaa, Acta Chem. Scand., 1957, 11, 247 CAS.
  5. P. Salomaa, Acta Chem. Scand., 1957, 11, 141; 235; 239 CAS.
  6. T. H. Fife, J. Am. Chem. Soc., 1965, 87, 271 CrossRef CAS.
  7. (a) P. Salomaa and S. Laiho, Acta Chem. Scand., 1963, 17, 103 CAS; (b) P. Salomaa, Suom. Kemistil. B, 1964, 37, 86 Search PubMed; (c) P. Salomaa and K. S. Sallinen, Acta Chem. Scand., 1965, 19, 1054 CAS; (d) P. Salomaa, Acta Chem. Scand., 1965, 19, 1263 CAS.
  8. P. D. Weeks and G. W. Zuorick, J. Am. Chem. Soc., 1969, 91, 477 CrossRef.
  9. P. D. Weeks, A. Grodski and R. Fanucci, J. Am. Chem. Soc., 1968, 90, 4958 CrossRef; D. P. Weeks, J. Cella and L. T. Chen, J. Org. Chem., 1972, 38, 3383.
  10. C. D. Hall and C. W. Goulding, J. Chem. Soc., Perkin Trans. 2, 1995, 1471 RSC.
  11. H. T. S. Britton, Hydrogen Ions, Chapman and Hall, London, 1955, Vol. 1 Search PubMed.
  12. A. Hussain, M. Yamuzaki and J. E. Truelove, J. Pharm. Sci., 1974, 63, 627 CAS.
  13. A. Hussain and J. E. Truelove, J. Pharm. Sci., 1979, 68, 235 CAS.
  14. A. Hussain, J. E. Truelove and A. Kostenbauder, J. Pharm. Sci., 1979, 68, 299 CAS.
  15. G. Akerlof and O. Short, J. Am. Chem. Soc., 1936, 58, 1241 CrossRef CAS.
  16. G. Kortum, W. Vogel and K. Andrussow, Dissociation Constants of Organic Acids in Aqueous Solution, Butterworths, London, 1961 Search PubMed.
  17. A. Kankaanperä and K. Miiki, Suom. Kemistil. B, 1968, 41, 42 Search PubMed.
  18. G.-A. Craze and A. J. Kirby, J. Chem. Soc., 1978, 354 Search PubMed.
  19. T. H. Fife and L. K. Jao, J. Am. Chem. Soc., 1968, 90, 4081 CrossRef CAS.
  20. J. L. Kurz, J. Am. Chem. Soc., 1963, 85, 987 CrossRef CAS.
  21. E. L. Eliel and C. A. Giza, J. Org. Chem., 1968, 33, 3754 CrossRef CAS.
  22. A. J. Kirby, The Anomeric Effect and Related Stereoelectronic Effects at Oxygen, Springer-Verlag, New York, 1983 Search PubMed.
  23. J. L. Jenson and W. B. Wuhrman, J. Org. Chem., 1983, 48, 4686 CrossRef.
  24. A. Brown and T. C. Bruice, J. Am. Chem. Soc., 1973, 95, 1593 CrossRef CAS.
  25. T. H. Fife, Acc. Chem. Res., 1972, 5, 264 CrossRef CAS.
  26. T. H. Fife and E. Anderson, J. Am. Chem. Soc., 1969, 91, 7163 CrossRef.
  27. T. H. Fife and L. H. Brod, J. Am. Chem. Soc., 1970, 92, 1681 CrossRef CAS.
  28. T. H. Fife and R. Bembi, J. Org. Chem., 1992, 57, 1295 CrossRef CAS.