Abstract and Summary
The two catalyst systems rhodium-triphenylphosphine and palladium chloride-triphenylphosphine were investigated for the respective hydroformylation and hydrocarboxylation of oleic acid or ester to produce C-19 bifunctional compounds. Compared to conventional cobalt carbonyl for making formylstearate, rhodium-triphenylphosphine permits lower pressures (1000–2000 psi vs. 3000–4000 psi), higher conversions (95% vs. 80%), and no loss of functionality (vs. 15% hydrogenation with cobalt). Although palladium chloride-triphenylphosphine for hydrocarboxylation introduces the carboxyl function directly into the fatty acid chain, CO pressures of 3000–4000 psi and corrosion-resistant equipment are necessary. When applied to polyunsaturated fatty acids, both rhodium and palladium catalyst systems have the outstanding advantage of introducing functionality at each double bond position to produce polyformyl- and polycarboxystearates. Selected formyl derivatives were converted in excellent yield to acetals, to acids and their esters, to hydroxymethyl compounds and their esters, and also to aminomethyl compounds that could be condensed to polyamides. Several of the esters and acetals were effective primary plasticizers for poly(vinyl chloride) that had outstanding low volatility characteristics. Other applications for these new and highly versatile derivatives included rigid urethane foams, urethane-modified coatings, ester lubricants, and a shrink-resist treatment for wool.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
“Fats and Oils Situation,” Economic Research Service, U.S. Department of Agriculture, Washington, DC, FOS278, June 1975, p. 19.
Ptyde, E.H., L.E. Gast, E.N. Frankel, K.D. Carlson, Polym. Plast. Technol. Eng. 7:1 (1976).
Falbe, J., “Carbon Monoxide in Organic Synthesis,” (Revised translation of the German edition 1967), Springer-Verlag, New York, 1970.
Paulik, F.E., Catal. Rev. 6:49 (1972).
Orchin, M., W. Rupilius, Catal. Rev. 6:85 (1972).
Pryde, E.H., E.N. Frankel, J.C. Cowan, JAOCS 49:451 (1972).
Frankel, E.N., S. Metlin, W.K. Rohwedder, I. Wender, Ibid. 46:133 (1969).
Frankel, E.N., Ibid. 53:138 (1976).
Frankel, E.N., Ibid. 48:248 (1971).
Frankel, E.N., Ann. N.Y. Acad. Sci. 214:79 (1973).
Frankel, E.N., F.L. Thomas, JAOCS 49:10 (1972).
Frankel, E.N., (Secretary of Agriculture) U.S. Patent 3,787,459 (January 22, 1974).
Frankel, E.N., F.L. Thomas, W.K. Rohwedder, Ind. Eng. Chem. Prod. Res. Dev. 12:47 (1973).
Frankel, E.N., F.L. Thomas, JAOCS 50:39 (1973).
Frankel, E.N., (Secreatry of Agriculture) U.S. Patent 3,928,231 (Dec. 23, 1975).
Frankel, E.N., F.L. Thomas, W.K. Rohwedder, Adv. Chem. Series No. 132, “Homogeneous Catalysis-II,” Am. Chem. Soc., Washington, DC, 1974, p. 145–165.
Frankel, E.N., F.L. Thomas, W.F. Kwolek, JAOCS 51:393 (1974).
Awl, R.A., E.N. Frankel, E.H. Pryde, J.C. Cowan, Ibid. 49:222 (1972).
Pryde, E.H., J.C. Cowan, in “Condensation Monomers,” Edited by J.K. Stille, John Wiley and Sons, Inc., New York, 1972, pp. 1–153.
Schwab, A.W., E.N. Frankel, E.J. Dufek, and J.C. Cowan, JAOCS 49:75 (1972).
Schwab, A.W., (Secretary of Agriculture) U.S. Patent 3,804,895 (April 16, 1974).
Schwab, A.W., JAOCS 50:74 (1973).
Dufek, E.J., R.O. Butterfield, and E.N. Frankel, 49:302 (1972).
Miller, W.R., W.E. Neff, E.N. Frankel, and E.H. Pryde, Ibid. 51:427 (1974).
Dufek, E.J., W.E. Parker, and R.E. Koos, Ibid. 51:351 (1974).
Kohlhase, W.L., Ibid. 52:444A, Abstr. 57 (1975).
Dufek, E.J., F.L. Thomas, and E.N. Frankel, Ibid. 53:198 (1976).
Awl, R.A., W.E. Neff, D. Weisleder, and E.H. Pryde, Ibid. 53:20 (1976).
Nielsen, A.T., and W.J. Houlihan, Org. React. 16:1 (1968).
Miller, W.R., and E.H. Pryde, JAOCS 53:150A, Abstr. 120 (1976).
Friedrich, J.P., G.R. List, and V.E. Sohns, Ibid. 50:455 (1973).
Friedrich, J.P., (Secretary of Agriculture), U.S. Patent 3,899,442 (August 12, 1975).
List, G.R., J.P. Friedrich, W.F. Kwolek, and C.D. Evans, JAOCS 50:210 (1973).
Awl, R.A., E.N. Frankel, and E.N. Pryde, Ibid. 53:190 (1976).
Friedrich, J.P., Ibid. 53:125 (1976).
Neff, W.E., R.A. Awl, E.H. Pryde, and J.C. Cowan, Ibid. 50:235 (1973).
Khoe, T.H., L.E. Gast, E.N. Frankel, and J.C. Cowan, Ibid. 49:134 (1972).
Khoe, T.H., and L.E. Gast, J. Paint Technol. 46:53 (1974).
Awl, R.A., E.N. Frankel, E.H. Pryde, and G.R. Riser, JAOCS 51:224 (1974).
Neff, W.E., E.N. Frankel, E.H. Pryde, Ibid. 53:152 (1976).
Frankel, E.N., W.E. Neff, F.L. Thomas, T.H. Khoe, E.H. Pryde, and G.R. Riser, Ibid. 52:498 (1975).
Kohlhase, W.L., E.N. Frankel, E.H. Pryde, and J.C. Cowan, Ibid. 50:301a, Abstr. 16 (1975).
Khoe, T.H., F.H. Otey, and E.N. Frankel, Ibid. 49:615 (1972).
Khoe, T.H., F. Otey, E.N. Frankel, and J.C. Cowan, Ibid. 50:331 (1973).
Khoe, T.H., and E.N. Frankel, Ibid. 53:17 (1976).
Lyon, C.K., V.H. Garrett, and E.N. Frankel, Ibid. 51:331 (1974).
Diamond, M.J., H.L. Needles, C.A. Elliger, D.J. Kertesz, E.N., Frankel, and G. Fuller, Ibid. 48:678 (1971).
Author information
Authors and Affiliations
About this article
Cite this article
Frankel, E.N., Pryde, E.H. Catalytic hydroformylation and hydrocarboxylation of unsaturated fatty compounds. J Amer Oil Chem Soc 54, A873–A881 (1977). https://doi.org/10.1007/BF02909059
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF02909059