Reaction control and potential tuning in a supercritical fluid

Abstract

A maximum is found in the ratio of endo- to exo- products vs. density in the Diels–Alder reaction between cyclopentadiene and methyl acrylate in supercritical carbon dioxide and is explained by the adjustment of the position of the nearest-neighbour solvent molecules with respect to the transition states.

References

1. B. L. Knutson, A. K. Dillow, C. L. Liotta and C. A. Eckert, in Innovations in supercritical fluids, ACS Symposium Series 608, ed. K. W. Hutchenson and N. R. Foster, American Chemical Society, Washington, 1995, p. 166.
2. D. Andrew, B. T. Des Islet, A. Margaritis and A. C. Weedon, J. Am. Chem. Soc., 1995, 117, 6132.
3. S. Kim and K. P. Johnston, Chem. Eng. Commun., 1988, 63, 49.
4. A. A. Clifford, in Supercritical fluids, ed. E. Kiran and J. M. H. Levelt Sengers, Kluwer, Amsterdam, 1994, 449.
5. J. A. Berson, Z. Hamlet and W. A. Mueller, J. Am. Chem. Soc., 1962, 84, 297.
6. H. D. Cochran and L. L. Lee, in Supercritical fluid science and technology, ACS Symposium Series 406, ed. K. P. Johnston and J. M. L. Penninger, American Chemical Society, Washington, 1988, p. 27.
7. R. D. Weinstein, A. R. Renslow, R. L. Danheiser, J. G. Harris and J. W. Tester, J. Phys. Chem., 1996, 100, 12337.