Effect of Aqueous PEG or PPG Solvents on Reaction Selectivity and Gibbs Energies

AIChE Journal

Volumn 50, Issue 2, 2004, Pages 511-517

  Leininger, Neil F ^a   Gainer, John L ^a   Kirwan, Donald J ^a  

^a UNIVERSITY OF VIRGINIA   (United States)

Author keywords

Environmentally benign solvents; Gibbs free energies; PEG 300; Polyglycols; PPG 425; Reaction kinetics

Indexed keywords

GIBBS FREE ENERGY; MOLECULAR WEIGHT; ORGANIC SOLVENTS; POLYPROPYLENES; RATE CONSTANTS; SOLUTIONS;

PRODUCT SELECTIVIES; REACTION SELECTIVITY;

POLYETHYLENE GLYCOLS;

MACROGOL; ORGANIC SOLVENT; POLYPROPYLENE; POLYPROPYLENE GLYCOL; SOLVENT; UNCLASSIFIED DRUG;

SOLVENT;

AQUEOUS SOLUTION; ARTICLE; CALCULATION; CHEMICAL REACTION KINETICS; DIELS ALDER REACTION; ENERGY; HYDROLYSIS;

BETULACEAE;

EID: 1642360205     PISSN: 00011541     EISSN: None     Source Type: Journal    
DOI: 10.1002/aic.10044     Document Type: Article

References (30)

1. Abraham, M. H., "Solvent Effects on Transition States and Reaction Rates," Progress in Physical Organic Chemistry, A. Streitwieser Jr. and R. W. Taft, eds., Interscience, New York, Vol. 11, p. 2 (1974).
2. Ahmad-Zadeh Samii, A., A. de Savignac, I. Rico and A. Lattes, "Diels-Alder Reaction of Cyclopentadiene and Methylacrylate as a Probe of Formamide Microemulsions," Tetrahedron, 41(18), 3683 (1985).
3. Blokzijl, W., M. J. Blandamer, and J. B. F. N. Engberts, "Diels-Alder Reactions in Aqueous Solutions. Enforced Hydrophobic Interactions between Diene and Dienophile," J. Am. Chem. Soc., 113(13), 4241 (1991).
4. Buncel, E., and H. Wilson, "Initial-State and Transition-State Solvent Effects on Reaction Rates and the Use of Thermodynamic Transfer Functions," Acc. Chem. Res. 12, 42 (1979).
5. Buncel, E., and H. Wilson, "Solvent Effects on Rates and Equilibria: A Practical Approach," J. of Chem. Education, 57(9), 629 (1980).
6. Cativiela, C., J. I. Garcia, J. A. Mayoral, and L. Salvatella, "Solvent Effects on Endo/Exo- and Regio-Selectivities of Diels-Alder Reactions of Carbonyl-Containing Dienophiles," J. Chem. Soc. Perkin Trans., 2, 847 (1994).
7. Cativiela, C., J. I. Garcia, J. A. Mayoral, and L. Salvatella, "Modeling of Solvent Effects on the Diels-Alder Reaction," Chem. Soc. Rev., 25, 209 (1996).
8. Chandler, K., C. L. Liotta, and C. A. Eckert, "Tuning Alkylation Reactions with Temperature in Near-Critical Water," AIChE J., 44(9), 2080 (1998).
9. DeWolfe, R. H., and W. G. Young, "Substitution and Rearrangement Reactions of Allylic Compounds," Chem. Rev., 56(2), 753 (1956).
10. DeWolfe, R. H., and W. G. Young, "Allylic Reactions," The Chemistry of Alkenes, S. Patai, ed., Interscience, New York, p. 681 (1964).
11. Engberts, J. B. F. N., "Diels-Alder Reactions in Water: Enforced Hydrophobic Interaction and Hydrogen Bonding," Pure Appl. Chem. 67(5), 823 (1995).
12. Fredenslund, A., and J. M. Sorensen, "Group Contribution Estimation Methods," Models for Thermodynamic and Phase Equilibrium Calculations, S. I. Sandler, ed., Marcel Dekker, New York, p. 287 (1994).
13. Haberfield, P., J. Friedman, and M. F. Pinkston, "Enhancement of Saponification Rates in Aqueous Dipolar Solvents: Hydroxide Ion Solvation vs Transition State Solvation," JACS, 94, 71 (1972).
14. Handbook of Chemistry and Physics, 63rd ed., p. C-256, CRC Press, Boca Raton, FL (1982).
15. Harris, J. M., "Introduction to Biotechnical and Biomedical Applications of Poly(Ethylene Glycol)," Poly(Ethylene Glycol) Chemistry: Biotechnical and Biomedical Applications, J. M. Harris, ed., Plenum Press, New York, p. 1 (1992).
16. Jenner, G., "Effect of Water on Chemo- and Endo-Selectivity in High Pressure Diels-Alder Furan Reactions. Hydrophobic or Polar Effects?," Tetrahedron Lett. 35(8), 1189 (1994).
17. Leininger, N. F. "Polyglycol-water Solutions as Benign Reaction Solvents," PhD Diss., University of Virginia (2002).
18. Leininger, N. F., R. Clontz, J. L. Gainer, and D. J. Kirwan, "Aqueous Polyglycol Solutions As Alternative Solvents," Clean Solvents: Alternative Media for Chemical Reactions and Processing, M. A. Abraham and L. Moens, eds., American Chemical Society, Washington, DC, ACS Symposium Series 819, p. 274 (2002).
19. Leininger, N. F., R. Clontz, J. L. Gainer, and D. J. Kirwan, "Polyethylene Glycol-Water and Polypropylene Glycol-Water Solutions as Benign Reaction Solvents," Chem. Eng. Comm., 190, 431 (2003).
20. Otto, S., W. Blokzijl, and J. B. F. N. Engberts, "Diels-Alder Reactions in Water. Effects of Hydrophobicity and Hydrogen Bonding," J. Org. Chem., 59, 5372 (1994).
21. Otto, S., and J. B. F. N. Engberts, "Diels-Alder Reactions in Water," Pure Appl. Chem., 72(7), 1365 (2000).
22. Rieger, M. M., "Cosmetics," Kirk-Othmer Encyclopedia of Chemical Technology, J. I. Kroschwitz and M. Howe-Grant, eds., Wiley, New York, Vol. 7, p. 572 (1991).
23. Rosa, R. G., L. Martinelli, L. H. M. Silva, and W. Loh, "Easy and Efficient Processes for Catalyst Recycling and Product Recovery in Organic Biphasic Systems Tested in the Hydrogenation of Hex-1-ene," Chem. Commun., 33 (2000).
24. Sherman, J., B. Chin, P. D. T. Huibers, R. Garcia-Valls, and T. A. Hatton, "Solvent Replacement for Green Processing," Environ. Health Perspect. 106, 253 (1998).
25. th ed., McGraw-Hill, New York (1996).
26. Tundo, P., P. T. Anastas, D. S. Black, J. Breen, T. Collins, S. Memoli, J. Miyamoto, M. Polyakoff, and W. Tumas, "Synthetic Pathways and Processes in Green Chemistry. Introductory Overview," Pure Appl. Chem., 72(7), 1207 (2000).
27. van der Wel, G. K., J. W. Wijnen, and J. B. F. N. Engberts, "Solvent Effects on a Diels-Alder Reaction Involving a Cationic Diene: Consequences of the Absence of Hydrogen-Bond Interactions for Accelerations in Aqueous Media," J. Org. Chem., 61, 9001 (1996).
28. nd ed., W. H. Freeman, New York (1994).
29. Watkins, K., "A Solvent Business," Chem. Eng. News, 80(2), 15 (2002).
30. Zalipsky, S., and J. M. Harris, "Introduction to Chemistry and Biological Applications of Poly(ethylene glycol)," Poly(ethylene glycol): Chemistry and Biological Applications, J. M. Harris and S. Zalipsky, eds., American Chemical Society, Washington, DC, p. 1 (1997).