Journal of the American Oil Chemists' Society

, Volume 89, Issue 6, pp 1113–1124 | Cite as

Rh-based Biphasic Isomerization of Carbon–Carbon Double Bonds in Natural Oils

Original Paper

Abstract

The biphasic conjugation of soybean and other natural oils, as well as the isomerization of various alkenes, was examined using a rhodium catalyst. A maximum yield, of conjugated soybean oil, of 96% was obtained when the reaction was run at 80 °C under argon with ethanol as the polar solvent, using triphenylphosphine monosulfonate sodium salt (tppms) as the ligand, and the surfactant sodium dodecyl sulfate (SDS). The optimized conditions were tested with other substrates, and the products were analyzed by 1H NMR, GC/MS, and ICP-MS.

Keywords

Conjugation Isomerization Soybean oil Rhodium Biphasic catalysis 

References

  1. 1.
    Arnet JE, Pettit R (1961) Rearrangement of dienes with iron pentacarbonyl. J Am Chem Soc 83:2954–2955CrossRefGoogle Scholar
  2. 2.
    Kuznik N, Krompiec S, Bieg T, Baj S, Skutil K, Chrobok A (2003) Double bond migration in S-allyl systems catalyzed by [RuClH(CO)(PPh3)3]. J Organomet Chem 665:167–175CrossRefGoogle Scholar
  3. 3.
    Dharmasena UL, Foucault HM, Santos EN, Fogg DE, Nolan SP (2005) N-Heterocyclic carbenes as activating ligands for hydrogenation and isomerization of unactivated olefins. Organometallics 24:1056–1058CrossRefGoogle Scholar
  4. 4.
    Coleto I, Roldan R, Jimenez-Sanchidrian C, Gomez JP, Romero-Salguero FJ (2010) Valorization of α-olefins: double bond shift and skeletal isomerization of 1-pentene and 1-hexene on zirconia-based catalysts. Catalysis Today 149:275–280CrossRefGoogle Scholar
  5. 5.
    Mitchell JH Jr, Kraybill HR (1942) Formation of conjugated material during bleaching of vegetable oils. J Am Chem Soc 64:988–994CrossRefGoogle Scholar
  6. 6.
    Jung MO, Yoon SH, Jung MY (2001) Effects of temperature and agitation rate on the formation of conjugated linoleic acids in soybean oil during hydrogenation process. J Agric Food Chem 49:3010–3016CrossRefGoogle Scholar
  7. 7.
    Simakova OA, Leino A, Campo B, Maki-Arvela P, Kordas K, Mikkola J, Murzin DY (2010) Linoleic acid isomerization over mesoporous carbon supported gold catalysts. Catalysis Today 150:32–36CrossRefGoogle Scholar
  8. 8.
    Meier MAR, Metzger JO, Schubert US (2007) Plant oil renewable resources as green alternatives in polymer science. Chem Soc Rev 36:1788–1802CrossRefGoogle Scholar
  9. 9.
    Wang C, Yang L, Ni B, Shi G (2009) Polyurethane networks from different soy-based polyols by the ring opening of epoxidized soybean oil with methanol, glycol, and 1, 2-propanediol. J Appl Polym Sci 114:125–131CrossRefGoogle Scholar
  10. 10.
    Andjelkovic DD, Valverde M, Henna P, Li F, Larock RC (2005) Novel thermosets prepared by cationic copolymerization of various vegetable oils—synthesis and their structure–property relationships. Polymer 46:9674–9685CrossRefGoogle Scholar
  11. 11.
    Larock RC, Dong X, Chung S, Reddy CK, Ehlers LE (2001) Preparation of conjugated soybean oil and other natural oils and fatty acids by homogeneous transition metal catalysis. J Am Oil Chem Soc 78:447–453CrossRefGoogle Scholar
  12. 12.
    Wexler H (1964) Polymerization of drying oils. Chem Rev 64:591–611CrossRefGoogle Scholar
  13. 13.
    Andjelkovic DD, Min B, Ahn D, Larock RC (2006) Elucidation of structural isomers from the homogeneous rhodium-catalyzed isomerization of vegetable oils. J Agric Food Chem 54:9535–9543CrossRefGoogle Scholar
  14. 14.
    Jain V, Proctor A (2007) Kinetics of photoirradiation-induced synthesis of soy oil-conjugated linoleic acid isomers. J Ag Food Chem 55:889–894CrossRefGoogle Scholar
  15. 15.
    Bergbreiter DE (2002) Using soluble polymers to recover catalysts and ligands. Chem Rev 102:3345–3384CrossRefGoogle Scholar
  16. 16.
    Lu J, Toy PH (2009) Organic polymer supports for synthesis and for reagent and catalyst immobilization. Chem Rev 109:815–838CrossRefGoogle Scholar
  17. 17.
    Lipshutz BH, Ghorai S (2008) Transition-metal-catalyzed cross-couplings going green: in water at room temperature. Aldrichimica Acta 41:59–72Google Scholar
  18. 18.
    Horvath IT (1998) Fluorous biphase chemistry. Acc Chem Res 31:641–650CrossRefGoogle Scholar
  19. 19.
    Joo F (2002) Aqueous biphasic hydrogenation. Acc Chem Res 35:738–745CrossRefGoogle Scholar
  20. 20.
    Ohlmann DM, Gooßen LJ, Dierker M (2011) Regioselective synthesis of β-aryl and β-amino substituted aliphatic esters by rhodium-catalyzed tandem double-bond migration/conjugate addition. Chem Eur J 17:9508–9519CrossRefGoogle Scholar
  21. 21.
    Ent AV, Onderdelinden AL (1990) Chlorobis(cyclooctene)rhodium(I) and -iridium(I) complexes. Inorg Synth 28:90–92CrossRefGoogle Scholar

Copyright information

© AOCS 2011

Authors and Affiliations

  1. 1.Department of ChemistryIowa State UniversityAmesUSA

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