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

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Organic Peroxygen Chemistry

Part of the book series: Topics in Current Chemistry ((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.

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Authors and Affiliations

  1. Institute of Technical Chemistry and Petrochemistry, Aachen University of Technology, D-5100, Aachen, FRG

    Siegfried Warwel, Michael Sojka & Mark Rüsch gen Klaas

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  1. Siegfried Warwel
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  2. Michael Sojka
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  3. Mark Rüsch gen Klaas
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Wolfgang A. Herrmann

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© 1993 Springer-Verlag

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Warwel, S., Sojka, M., Klaas, M.R.g. (1993). Synthesis of dicarboxylic acids by transition-metal catalyzed oxidative cleavage of terminal-unsaturated fatty acids. In: Herrmann, W.A. (eds) Organic Peroxygen Chemistry. Topics in Current Chemistry, vol 164. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3-540-56252-4_26

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  • DOI: https://doi.org/10.1007/3-540-56252-4_26

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