Synthesis of alkyl‐branched fatty acids

Alkyl‐branched fatty compounds are of interest for industrial products in the cosmetics and lubricant areas. In this review, clay‐ and zeolite‐catalyzed isomerizations of unsaturated fatty compounds, especially of oleic acid, are discussed. While clay‐catalyzed reactions give most complex mixtures of dimeric fatty acids and of monomeric so‐called “isostearic acid”, the zeolite‐catalyzed process yields preferentially an isomeric mixture of isostearic acids having the methyl branch on the 8–14 positions of the alkyl chain. Synthetically useful additions of alkyl radicals can only be performed on ω‐unsaturated fatty compounds, whereas perfluoroalkyl iodides were added to fatty compounds with terminal as well as internal double bonds using electron transfer‐initiated radical addition reactions. Electrophilic additions of alkyl carbenium ions generated by decomposition of alkyl chloroformates by ethylaluminum sesquichloride give well‐defined alkyl‐branched oleochemicals with good yields.