Selective Oxidation and Oxidative Cleavage
of Unsaturated Fatty Compounds
Arno Behr, Nils Tenhumberg, A. Wintzer, Technische Universität Dortmund, 
Dortmund, Germany

Fats and oils are very important renewables which are produced worldwide in more than 160 million tons/year. On the basis of these natural sources already a great number of oleochemicals like surfactants and lubricants is built, but in chemical industry there is still a great effort to look for further functionalisations to get higher value-added products. 
One fundamental way of derivatisation is the catalytic oxidation of unsaturated oleo compounds getting fatty epoxides and bishydroxides or a cleavage of the CC double bond thus obtaining two short chain carboxylic compounds. In the present contribution a systematic investigation of the catalytic oxidation of methyl oleate will be presented:
•	the ruthenium- and molybdenum catalysed epoxidation to 9,10-epoxy stearate with hydrogen peroxide and tert.-butyl hydroperoxide as oxidants [1]
•	the oxidative cleavage with hydrogen peroxide as oxidant using a ruthenium – dipicolinic acid catalyst yielding azelaic acid methyl ester in amounts of 86% [2]
•	the oxidative cleavage of 9,10-dihydroxy stearate with oxygen using the catalyst system cobalt acetylacetonate / N-hydroxyphthalimid [3]
The products formed are of high interest for the chemical industry: The fatty epoxides can be used as starting material for epoxy resins or as intermediates for polyurethane-polyols. Azelaic acid, which is used in the manufacture of polyamides, adhesives and plasticisers, is so far only produced via expensive and dangerous ozonolysis. Now an easy and economical way to azelaic acid has been developed via homogeneous transition metal catalysis. The investigation of the reaction pathway showed that the reaction proceeds via a tandem reaction of epoxidation and hydrolysis of the epoxide and oxidative cleavage of the vicinal diol. 

[1] A. Behr, N. Tenhumberg, A. Wintzer, Eur. J. Lipid Sci. Technol. 2012, 114, 905-910
[2] A. Behr, N. Tenhumberg, A. Wintzer, RSC Advances, 2013, 3, 172-180
[3] A. Behr, N. Tenhumberg, Chem. Ing. Tech. 2012, 84, 1559-1567