|Solaiman, Daniel - Dan|
Submitted to: Journal of the American Oil Chemists' Society
Publication Type: Peer reviewed journal
Publication Acceptance Date: 3/17/2014
Publication Date: 4/1/2014
Citation: Zerkowski, J.A., Solaiman, D. 2014. 2-Fatty acrylic acids: new highly derivatizable lipophilic platform molecules. Journal of the American Oil Chemists' Society. DOI: 10.1007/s11746-014-2459-5. Interpretive Summary: Fats and oils derived from agricultural commodities have been the object of many chemical modifications over the years, with the aim of increasing their usability in a variety of technological situations. As the global economy attempts to transition from dependence on petroleum products and more toward renewable bio-derived feedstocks, this kind of chemical manipulation will only gain in importance. The rules of chemistry impose some limits, however, to the kinds of changes that are performable on fats and oils as they occur naturally. This paper reports a new modification of fatty acids that opens the door to a wealth of subsequent chemistry. We began by inserting a single new chemical group, at one site of the fatty acid skeleton. The special feature of this unit is that it serves as a springboard to adding other new groups (naturally occurring amino acids are one example) so that the structural diversity of the fatty acid skeleton can be greatly enhanced. The chemical transformations involved are in general straightforward to perform, and proceed in good yields. As a result, these hybrid fat and oil derivatives will find new opportunities for use as bio-based building blocks for detergents, lubricants, and polymers.
Technical Abstract: This paper reports the incorporation of an alpha-methylene unit into fatty acid skeletons. Since the new olefin is conjugated with the carboxylate, it is susceptible to 1,4- (Michael) additions. We have used multifunctional thiols and amines for additions at the methylene. The resulting products possess clusters of functionality grouped at one end of a hydrophobic tail. These structural patterns will be of use in the design of new types of bio-based surfactants and polymers. One particularly promising pattern of functionality that can be obtained through oxidation and reduction chemistry is a 2-fatty 1,2,3-propanetriol, or a lipophilized glycerol moiety.