PRODUCTS OF THE DIMERIZATION OF UNSATURATED FATTY-ACIDS .9. KINETIC-STUDIES ABOUT THE DIMERIZATION OF LINOLEIC-ACID

To clarify the dimerisation process of linoleic acid, we investigated samples taken in different time intervals. The first reaction step is a water addition at double bonds of the starting material and not double bond isomerisation as previously assumed. The resulting unsaturated monohydroxy fatty acids can cyclize with the second double bond in an intramolecular reaction forming 2,5-disubstituted tetrahydrofuran respectively 2,6-disubstituted tetrahydropyran derivates. Linolenic acid, present nearly always in small amounts in linoleic acid, reacts to first dimerisation products with linoleic acid by formation of a C-C-bond. The aliphatic dimers cyclize in an intramolecular reaction to monocyclic compounds. No dimeric acids, which would result from a Diels-Alder-reaction, could be identified. Bicyclic and aromatic dimeric acids can also be found in the early phase of the dimerisation. In the further progress of the reaction isomerisations, hydrogenations and dehydrogenations of the primary reaction products occur, thus the content of aromatic substances increases steadily.