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Comparison of Reactivity in the Cross Metathesis of Allyl Acetate-Derivatives with Oleochemical Compounds

Abstract

The metathesis of unsaturated oleochemicals is an excellent tool for generating α,ω-difunctional substrates, which are useful intermediates for polymer synthesis. This article describes the cross metathesis of allyl acetate and cis-1,4-diacetoxy-2-butene with methyl 10-undecenoate and methyl oleate, which are oleochemical key substrates. Detailed optimizations led to high conversion rates and yields of the desired products under mild reaction conditions by using a low concentration of commercially available homogeneous ruthenium catalysts.

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References

  1. Hill K (2000) Fats and oils as oleochemical raw materials. Pure Appl Chem 72:1255–1264

    Article  CAS  Google Scholar 

  2. Mutlu H, Meier MAR (2010) Castor oil as a renewable resource for the chemical industry. Eur J Lipid Sci Technol 112:10–30

    Article  CAS  Google Scholar 

  3. Rybak A, Meier MAR (2007) Cross-metathesis of fatty acid derivatives with methyl acrylate: renewable raw materials for the chemical industry. Green Chem 9:1356–1361

    Article  CAS  Google Scholar 

  4. Rybak A, Meier MAR (2008) Cross-metathesis of oleyl alcohol with methyl acrylate: optimization of reaction conditions and comparison of their environmental impact. Green Chem 10:1099–1104

    Article  CAS  Google Scholar 

  5. Jacobs T, Rybak A, Meier MAR (2009) Cross-metathesis reactions of allyl chloride with fatty acid methyl esters: efficient synthesis of α,ω-difunctional chemical intermediates from renewable raw materials. Appl Catal A: Gen 353:32–35

    Article  CAS  Google Scholar 

  6. Malacea R, Fischmeister C, Bruneau C, Dubois JL, Couturier JL, Dixneuf PH (2009) Renewable materials as precursors of linear nitrile-acid derivatives via cross-metathesis of fatty esters and acids with acrylonitrile and fumaronitrile. Green Chem 11:152–155

    Article  CAS  Google Scholar 

  7. Miao X, Fischmeister C, Bruneau C, Dixneuf PH (2009) A direct route to bifunctional aldehyde derivatives via self- and cross-metathesis of unsaturated aldehydes. Chem Sus Chem 2:542–545

    Article  CAS  Google Scholar 

  8. Ho TTT, Jacobs T, Meier MAR (2009) A design-of-experiments approach for the optimization and understanding of cross-metathesis reaction of methyl ricinoleate with methyl acrylate. Chem Sus Chem 2:749–754

    Article  CAS  Google Scholar 

  9. Djigoue GB, Meier MAR (2009) Improving the selectivity for the synthesis of two renewable platform chemicals via olefin metathesis. Appl Catal A: Gen 368:158–162

    Article  CAS  Google Scholar 

  10. Miao X, Blokhin A, Pasynskii A, Nefedov S, Osipov SN, Roisnel T, Bruneau C, Dixneuf PH (2010) Alkylidene-Ruthenium-Tin catalysts for the formation of fatty nitriles and esters via cross-metathesis of plant oil derivatives. Organometallics 29:5257–5262

    Article  CAS  Google Scholar 

  11. Miao X, Dixneuf PH, Fischmeister C, Bruneau C (2011) A green route to nitrogen-containing groups: the acrylonitrile cross-metathesis and applications to plant oil derivatives. Green Chem 13:2258–2271

    Article  CAS  Google Scholar 

  12. Miao X, Malacea R, Fischmeister C, Bruneau C, Dixneuf PH (2011) Ruthenium-alkylidene catalyzed cross-metathesis of fatty acid derivatives with acrylonitrile and methyl acrylate: a key step toward long-chain bifunctional and amino acid compounds. Green Chem 13:2911–2919

    Article  CAS  Google Scholar 

  13. Behr A, Perez Gomes J (2011) The cross-metathesis of methyl oleate with cis-2-butene-1,4-diyl diacetate and the influence of protecting groups. Beilstein J Org Chem 7:1–8

    Article  CAS  Google Scholar 

  14. Biermann U, Meier MAR, Butte W, Metzger JO (2011) Cross-metathesis of unsaturated triglycerides with methyl acrylate: synthesis of a dimeric metathesis product. Eur J Lipid Sci Technol 113:39–45

    Article  CAS  Google Scholar 

  15. Behr A, Perez Gomes J, Bayrak Z (2011) Cross-metathesis of methyl 10-undecenoate with diethyl maleate: formation of an α,ω-diester via a metathesis reaction network. Eur J Lipid Sci Technol 113:189–196

    Article  CAS  Google Scholar 

  16. Abbas M, Slugovc C (2012) Optimized reaction conditions for the cross-metathesis of methyl oleate and oleylamine with ethyl acrylate. Monatsheft Chemie 143:669–673

    Article  CAS  Google Scholar 

  17. Mol JC (1994) Metathesis of unsaturated fatty acid esters and fatty oils. J Mol Catal 90:185–199

    Article  CAS  Google Scholar 

  18. Svensson M (2010) Surfactants based on natural fatty acids. In: Kjellin M, Johansson I (eds) Surfactants from renewable resources. Wiley, New York, pp 3–15

    Google Scholar 

  19. Warwel S, Tillack J, Demes C, Kunz M (2001) Polyesters of ω-unsaturated fatty acid derivatives. Macromol Chem Phys 202:1114–1121

    Article  CAS  Google Scholar 

  20. Yadav GD, Doshi NS (2002) Development of a green process for poly-α-olefin based lubricants. Green Chem 4:528–540

    Article  CAS  Google Scholar 

  21. Keitz BK, Endo K, Herbert MB, Grubbs RH (2011) Z-selective homodimerization of terminal olefins with a ruthenium metathesis catalyst. J Am Chem Soc 133:9686–9688

    Article  CAS  Google Scholar 

  22. Arjona O, Csaky AG, Murcia MC, Plumet J (2000) Regioselective domino metathesis of 7-oxanorbornene derivatives as a new stereoselective entry into 2,6-dioxabicyclo[4.3.0]nonenes. Tetrahedron Lett 41:9777–9779

    Article  CAS  Google Scholar 

  23. Sano K, Maki K, Kamei H (1991) Process for preparation of allyl acetate US Patent 5,011,980

  24. Heumann A, Akermark B (1984) Oxidation von Palladiumsalzen: katalytische Herstellung von Allyacetaten aus Monoolefinen mit einem Dreikomponenten-Oxidationssystem. Angew Chem 96:443–444

    Article  CAS  Google Scholar 

  25. Churi RJ, Subrahmanyam VVR (1993) A study of metathesis of unsaturated carboxylic esters. J Oil Technol Ass India 25:93–95

    CAS  Google Scholar 

  26. Blackwell HE, O’Leary DJ, Chatterjee AK, Washenfelder RA, Bussmann DA, Grubbs RH (2000) New approaches to olefin cross-metathesis. J Am Chem Soc 122:58–71

    Article  CAS  Google Scholar 

  27. von Czapiewski M, Kreye O, Mutlu H, Meier MAR (2013) Cross-metathesis versus palladium-catalyzed C-H-activation: acetoxy ester functionalization of unsaturated fatty acid methyl esters. Eur J Lipid Sci Technol 115:76–85

    Article  Google Scholar 

  28. Allaert B, Dietliens N, Ledoux N, Vercaemst C, van der Voort P, Stevens CV, Verpoort F (2006) Synthesis and activity for ROMP of bidentate Schiff base substituted second generation Grubbs catalysts. J Mol Cat A: Chem 260:221–226

    Article  CAS  Google Scholar 

  29. Ledoux N, Drozdzak R, Allaert B, Linden A, van der Voort P, Verpoort F (2007) Exploring new synthetic strategies in the development of a chemically activated Ru-based olefin metathesis catalyst. Dalton Trans 44:5201–5210

    Article  Google Scholar 

  30. Clavier H, Nolan SP (2007) N-heterocyclic carbene and phosphine ruthenium indenylidene precatalysts: a comparative study in olefin metathesis. Chem Eur J13:8029–8036

    Article  Google Scholar 

  31. Weskamp T, Kohl FJ, Hieringer W, Gleich D, Herrmann WA (1999) Hochaktive Rutheniumkatalysatoren für die Olefinmetathese: die Synergie N-heterocyclischer Carbene und koordinativ labiler Liganden. Angew Chem 111:2573–2576

    Article  Google Scholar 

  32. Straub BF (2005) Origin of the high activity of second-generation grubbs catalysts. Angew Chem Int Ed 44:5974–5978

    Article  CAS  Google Scholar 

  33. Behr A, Krema S, Kämper A (2012) Ethenolysis of ricinoleic acid methyl ester—an efficient way to the oleochemical key substance methyl dec-9-enoate. RSC Adv 2:12775–12781

    Article  CAS  Google Scholar 

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Acknowledgments

This work was supported financially by the German Federal Ministry of Food, Agriculture and Consumer Protection (represented by the Fachagentur Nachwachsende Rohstoffe) and the Emery Oleochemicals GmbH. The authors would like to thank Umicore AG & Co. KG and Evonik Industries for their donations of ruthenium metathesis catalysts.

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Correspondence to Arno Behr.

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Behr, A., Toepell, S. Comparison of Reactivity in the Cross Metathesis of Allyl Acetate-Derivatives with Oleochemical Compounds. J Am Oil Chem Soc 92, 603–611 (2015). https://doi.org/10.1007/s11746-015-2614-7

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  • DOI: https://doi.org/10.1007/s11746-015-2614-7

Keywords

  • Oleochemistry
  • Metathesis
  • Homogeneous catalysis
  • Allyl acetate
  • cis-1,4-Diacetoxy-2-butene
  • Methyl oleate
  • Methyl 10-undecenoate