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United States Department of Agriculture

Agricultural Research Service

Research Project: FUNCTIONALIZATION OF VEGETABLE OILS FOR USE IN THE POLYMER, OLEOCHEMICAL, AND LUBRICANT INDUSTRIES

Location: Bio-oils Research Unit

Title: Bismuth(III) trifluoromethanesulfonate catalyzed ring opening reaction of mono epoxy oleochemicals to form keto and diketo derivatives

Authors
item Doll, Kenneth
item Bantchev, Grigor
item Murray, Rex

Submitted to: ACS Sustainable Chemistry & Engineering
Publication Type: Peer Reviewed Journal
Publication Acceptance Date: November 26, 2012
Publication Date: January 7, 2013
Citation: Doll, K.M., Bantchev, G.B., Murray, R.E. 2013. Bismuth(III) trifluoromethanesulfonate catalyzed ring opening reaction of mono epoxy oleochemicals to form keto and diketo derivatives. ACS Sustainable Chemistry & Engineering. 1:39-45.

Interpretive Summary: The use of chemistry to turn natural oil into valuable materials is of great importance for the materials of the future. Ketones are a class of chemical molecule that find use in solvents and coatings that people use every day, i.e. fingernail polish remover. Although ketones have been made previously from vegetable oil, the processes used require either complicated biological systems or strong oxidation chemicals. Our new system uses only a small amount of a bismuth salt to accomplish the same chemistry. This produces a high yield of an effective product with minimal costs in order to benefit everyone from the vegetable oil industry to the end consumer.

Technical Abstract: Using a catalytic system, methyl oleate is transformed into long chain keto and diketo derivatives via an epoxide route. Methyl 9(10)-oxooctadecanoate and methyl 9,10-dioxooctadecanoate were made by a ring opening reaction of epoxidized methyl oleate using bismuth triflate catalyst. Lower reaction temperatures favor the mono-ketone whereas higher temperatures are required to produce the diketone. The second synthesis also requires the use of dimethylsulfoxide to serve as an oxygen atom donor and is also needed to keep the catalyst in its active form. The ketone was also evaluated as a lubricity additive in soybean oil where it was found that it reduced wear, but did not improve oxidative stability. This drawback, while not good in lubricant formulations, is desirable in many applications such as paints and linoleum productions and also makes these materials potential substrates for further derivatizations such as the Bayer Villiger reaction. Overall, this is an effective synthesis of promising materials, with high biobased content, useful for industries of the future.

Last Modified: 10/24/2014
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