Ketofettsäure‐Derivate – Ein einfaches Verfahren zu ihrer Herstellung

Abstract

The alkylaluminium halide induced Friedel-Crafts acylation of unsaturated fatty compounds and acyl chlorides give the corresponding P,y-unsaturated ketones. Very interesting products are obtained by the acylation of unsaturated fatty acids and succinic anhydride. By this reaction a carbonyl and a carboxyl function can be introduced to the molecule chain of the fatty compound. L i t e r a t u r e '

Solvent‐ and Metal‐Free Ketonization of Fatty Acid Methyl Esters and Triacylglycerols with Nitrous Oxide

“…[2][3][4] Poly-ketone products also have an interesting potential as environmentally friendly lubricants, adhesives and additives in, e.g., PVC processing. [1][2][3][4][5][6][7] Although several keto fatty acids can be found in nature, only licanic acid (4-keto-Z,E,E-9,11,13-octadecatrienoic acid) can be obtained in sig-nificant amounts from natural sources. Many microorganisms are known for their selective oxidation of fatty acids, albeit often at a relatively low rate.…”

“…The oxyfunctionalization of fatty acids is also possible via a two-step process in which the unsaturated bond is first epoxidized and the epoxide subsequently isomerized. [7,8] Fatty epoxides are produced in more than 350,000 tons/year and are mainly used as stabilizing plasticizers in PVC processing. [15] While peracids are commonly used as the stoichiometric oxidant for the first step, recent reports focus on the development of a (bio)catalytic process with commercial H 2 O 2 or alkyl hydroperoxides.…”

“…[16][17][18][19][20][21] Three important isomerization strategies are reported, viz., reaction in alkaline [22] or acidic conditions, [23] and nucleophilic catalysis. [24] The inability of the aforementioned isomerization methods to selectively produce poly-ketones from poly-epoxides should be stressed. Ketalization of ketones with neighbouring epoxides may give rise to the formation of intra-and intermolecular cyclic ethers.…”

“…The volume-time yield of 85 g L À1 h À1 is one order of magnitude higher than that obtained with conventional Wacker chemistry. [7,11] 13 C NMR on the non-purified sample reveals a 212 ppm signal which must be assigned to a keto carbon, R À C(=O) À R', rather than an aldehyde, since it is not observed in the 1358 DEPT 13 C NMR spectrum (see Supporting Information). The protons in a-positions to the ketone group, À CH 2 À C(=O) À CH 2 À , occur as a multiplet in the 1 H NMR spectrum with a resonance at 2.43 ppm.…”

“…The ketone product shows a well-defined melting point at 47 8C in a differential scanning calorimetry (DSC) experiment (see Supporting Information), in accordance with the melting-point range published in the literature. [7] In addition to the absence of solvent and catalyst, this new chemistry allows tuning of the alkene conversion with parameters such as N 2 O partial pressure and reaction time.…”