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Synthesis of dicarboxylic acids by transition-metal catalyzed oxidative cleavage of terminal-unsaturated fatty acids

  • Siegfried Warwel
  • Michael Sojka
  • Mark Rüsch gen Klaas
Chapter
Part of the Topics in Current Chemistry book series (TOPCURRCHEM, volume 164)

Abstract

9-Decenoic- and 13-tetradecenoic methylesters, obtained by Re-catalysed metathesis of natural C18- and C22-fatty esters with ethylene as well as the industrially produced 10-undecenoic methylester were used as starting materials for the preparation of dicarboxylic esters. Two different reaction routes were applied. Ketonisation of the terminal unsaturated fatty acid esters by Wacker-oxidation using PdCl2/CuCl or RhCl3/FeCl3 as catalysts led to methyl keto-fatty acid esters, which were oxidatively cleaved by Mn-catalysed oxidation with air at 115 °C to mixtures of C8-/C9-, C9-/C10- and C12-/C13-dicarboxylic monomethylesters with conversion rates and selectivities of 90%.

Pure C9-, C10- and C13-dicarboxylic acids were achieved in isolated yields of 80–90% by an one step oxidative cleavage of the terminal unsaturated fatty acids with peracetic acid as oxidant and different ruthenium compounds e.g. Ru(acac)3 as catalysts. Starting with 10-undecenoic acid, a simple catalyst recycling could be established.

Replacing peracetic acid with H2O2 or acetic acid/H2O2 the ruthenium-catalyzed oxidative cleavage of C=C-bonds did not proceed because of an unproductive decomposition of H2O2. With Re2O7 as catalyst hardly any decomposition of H2O2 took place and using 1,4-dioxane as solvent, olefins were converted to vicinal diols in fair yields.

Keywords

Dicarboxylic Acid Erucic Acid Peracetic Acid Oxidative Cleavage Olefin Metathesis 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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Copyright information

© Springer-Verlag 1993

Authors and Affiliations

  • Siegfried Warwel
    • 1
  • Michael Sojka
    • 1
  • Mark Rüsch gen Klaas
    • 1
  1. 1.Institute of Technical Chemistry and PetrochemistryAachen University of TechnologyAachenFRG

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