ARS | Publication request: SYNTHESIS OF HALOHYDRINS AND HALOETHERS FROM OLEATES

Submitted to: American Oil Chemists' Society Meeting
Publication Type: Abstract Only
Publication Acceptance Date: May 3, 2006
Publication Date: May 3, 2006
Citation: Isbell, T., Lowery, B.A. 2006. Synthesis of halohydrins and haloethers from oleates [abstract]. American Oil Chemists' Society Meeting. p. 74.

Technical Abstract: Utilization of triglycerides and fatty acids typically require derivatization to improve their performance as lubricants. Increasing the saturation in the molecule will improve the oxidative stability of the fat but results in an increase in the pour point (the point at which a liquid can be cooled and still pour, the lower the pour point the better the performance). By increasing the branching in the molecule the pour point is decreased through steric interactions at the branch point which disrupts crystal formation. The fat molecule can be modified at the olefin position to both increase branching and saturation improving oxidative stability and pour points. We explored reactions that insert branching via oxidation of the olefin to a haloether using hypohalites. Halogen in a +1 oxidation state was used to drive the reactions, which were initially run using methyl oleate as a model. A variety of reaction conditions and means of forming X+ in situ were tested for the formation of haloethers. High yields of haloethers were obtained when reactions were conducted in alkanols. Both branched and primary alcohols reacted smoothly but only low yields were observed with secondary alcohols. The haloethers could be subsequently reduced using a pladium catalyst to yield the corresponding saturated ethers with near quantitative yields for the removal of chlorine.