The Acrylation of Glycerol: A Precursor to Functionalized Lipids

Abstract

With the objective of expanding the number of functionalized lipids available, the reactive vinyl group of acrylic acid was introduced to triacylglycerol by esterification of glycerol. Didecanoylacryloylglycerol was synthesized from decanoic and acrylic acids and glycerol using K 2 O as catalyst. 2 g (21.7 mmol) glycerol, 11.3 g (65.4 mmol) decanoic acid, 6.2 g (86.1 mmol) acrylic acid, 60 ml hexane, and 400 mg K 2 O were added to 300-ml closed stainless steel reactor and maintained at 200°C for 5 h. The resulting product, designated DDA, was isolated at about 40% yield based on the acylglycerol products. The other products included tridecanoylglycerol, diacryloyldecanoylglycerol, and the diacylglycerols of these acids. DDA was then converted to functionalized lipids by the Michael addition and Heck reaction. The Michael addition of thiophenol and 4-bromothiophenol yielded the corresponding linear thioethers whereas and Heck reaction products from bromobenzene and bromoanisole yielded triacylglycerols containing trans-cinnamic acid and trans-(4-methoxy)cinnamic acid, respectively. Keywords Acrylation Á Heck reaction Á Functionalized lipids Á Base catalysis Á Thioether Á Michael addition Abbreviations DDA 1,2-Didecanoyl-3-acrylylglycerol DAD 1,3-Didecanoyl-2-acrylylglycerol DAA Decanoyldiacrylylglycerol, position nonspecific DDD Tridecanoin DD Didecanoin diglyceride, position nonspecific DA Diglyceride of decanoic and acrylic acids, position nonspecificMention of trade names or commercial products in this publication is solely for the purpose of providing specific information and does not imply recommendation or endorsement by the U.S. Department of Agriculture. USDA is an equal opportunity provider and employer.