ARS | Publication request: Synthesis of Halohydrins and Haloethers from Oleates

Submitted to: Great Lakes Regional American Chemical Society Symposium
Publication Acceptance Date: September 13, 2004
Publication Date: October 20, 2004
Citation: Isbell, T., Mund, M.S., Edgcomb, M.R., Green, L.A., Lowery, B.A. 2004. Synthesis Of Halohydrins And Haloethers From Oleates. Great Lakes Regional American Chemical Society Symposium.

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 through an oxidative halohydrin using hypohalites. Iodine 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 I+ in situ were tested for the formation of haloethers and ketones. Both I- and I2 were used as catalytic oxidizing agents with aqueous NaOCl used as a re-oxidant. 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. When ethyl acetate and water were used as solvent, high yields of ketones were observed after 24 hours at reflux.