Abstract
1,3-Diacylglycerols were synthesized by direct esterification of glycerol with free fatty acids in a solvent-free system. Free fatty acids with relatively low melting points (<45°C) such as unsaturated and medium-chain saturated fatty acids were used. With stoichiometric ratios of the reactants and water removal by evaporation at 3 mm Hg vacuum applied at 1 h and thereafter, the maximal 1,3-diacylglycerol content in the reaction mixture was: 84.6% for 1,3-dicaprylin, 84.4% for 1,3-dicaprin, 74.3% for 1,3-dilinolein, 71.7% for 1,3-dieicosapentaenoin, 67.4% for 1,3-dilaurin, and 61.1% for 1,3-diolein. Some of the system’s parameters (temperature, water removal, and molar ratio of the reactants) were optimized for the production of 1,3-dicaprylin, and the maximal yield reached 98%. The product was used for the chemical synthesis of 1,3-dicapryloyl-2-eicosapentaenoylglycerol. The yield after purification was 42%, and the purity of the triacylglycerol was 98% (both 1,3-dicapryloyl-2-eicosapentaenoylglycerol and 1,2-dicapryloyl-3-eicosapentaenoylglycerol included) by gas chromatographic analysis, of which 90% was the desired structured triacylglycerol (1,3-dicapryloyl-2-eicosapentaenoylglycerol) as determined by silver ion high-performance liquid chromatographic analysis.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Berger, M., and M.P. Schneider, Regioisomerically Pure Mono and Diacylglycerols as Synthetic Building Blocks, Fat Sci. Technol. 95:169–175 (1993).
Haftendorn, R., and R. Ulbrich-Hofmann, Synthesis of 2-Modified 1,3-Diacylglycerols, Tetrahedron 51:1177–1186 (1995).
El Kihel, L., J. Bourass, P. Richomme, J.Y. Petit, and Y. Letourneux, Synthesis and Evaluation of the Anti-inflammatory Effects of Niflumic Acid Lipophilic Prodrugs in Brain Edema, Drug. Res. 46:1040–1044 (1996).
Mantelli, S., P. Speiser, and H. Hauser, Phase Behavior of Diglyceride Prodrugs: Spontaneous Formation of Unilamellar Vesicles, Chem. Phys. Lipids 37:329–343 (1985).
Scriba, G.K.E., Phenytoin-Lipid Conjugates as Potential Prodrugs of Phenytoin, Arch. Pharm. 326:477–481 (1993).
Soberg Christensen, M., C.E. Høy, C.C. Becker, and T.G. Redgrave, Intestinal Absorption and Lymphatic Transport of Eicosapentaenoic (EPA). Docosahexaenoic (DHA), and Decanoic Acids: Dependence on Intramolecular Triacylglycerol Structure, Am. J. Clin. Nutr. 61:56–61 (1995).
Ikeda, I., X.-P. Gu, I. Miyamoto, and M. Okahara, Preparation of 1,3-Diacylglycerols and 1-Alkyl-3-acylglycerols in the Presence of Quaternary Ammonium Salt, J. Am. Oil Chem. Soc. 66: 822–824 (1989).
Benbouzid, M., A. Bhati, and J.R. Hamilton, Synthesis of Symmetrical Diacid Triacylglycerols from Glycerol-1,3-ditosylate, Fat Sci. Technol. 90:292–295 (1988).
Jensen, R.G., and R.E. Pitas, Synthesis of Some Acylglycerols and Phosphoglycerides, in Advances in Lipid Research, Vol. 14, edited by R. Paoletty and D. Kritchevsky, Academic Press, New York, 1976, p. 228.
Yamane, T., S.T. Kang, K. Kawahara, and Y. Koizumi, High-Yield Diacylglycerol Formation by Solid-Phase Enzymatic Glycerolysis of Hydrogenated Beef Tallow, J. Am. Oil Chem. Soc. 71:339–342 (1994).
Berger, M., K. Laumen, and M.P. Schneider, Enzymatic Esterification of Glycerol I. Lipase-Catalyzed Synthesis of Regioisomerically Pure 1,3-sn-Diacylglycerols, Ibid.:955–960 (1992).
Waldinger, C., and M.P. Schneider, Enzymatic Esterification of Glycerol III. Lipase-Catalyzed Synthesis of Regioisomerically Pure 1,3-sn-Diacylglycerols and 1(3)-rac-Monoacylglycerols Derived from Unsaturated Fatty Acids, Ibid.:1513–1519 (1996).
Haraldsson, G.G., B.O. Gudmundsson, and O. Almarsson, The Synthesis of Homogeneous Triglycerides of Eicosapentaenoic Acid and Docosahexaenoic Acid by Lipase, Tetrahedron 51: 941–952 (1995).
Tatara, T., T. Fujii, T. Kawase, and M. Minagawa, Determination of Tri-, Di-, Monooleins, and Free Oleic Acid by the Thin-Layer Chromatography-Flame Ionization Detector System Using Internal Standards and Boric Acid Impregnated Chromarods, Lipids 18:732–736 (1983).
Baba, N., N. Hirota, H. Umino, K. Matsuo, S. Nakajima, S. Tahara, T. Kaneko, and M. Matsuo, Synthesis of Triacylglyceride Hydroperoxides Derived from Linoleic Acid, Biosci. Biotechnol. Biochem. 58:1547–1548 (1994).
Srisiri, W., H.G. Lamparski, and D.F. O’Brien, Syntheses of Polymerizable Monoacylglycerols and 1,2-Diacyl-sn-glycerols, J. Org. Chem. 61:5911–5915 (1996).
Han, J.J., Y. Iwasaki, and T. Yamane, Monitoring of Lipase-Catalyzed Transesterification Between Eicosapentaenoic Acid Ethyl Ester and Tricaprylin by Silver Ion High-Performance-Liquid Chromatography and High-Temperature Gas Chromatography, J. Am. Oil Chem. Soc. 76:31–39 (1999).
Miller, C., H. Austin, L. Posorske, and J. Gonzlez, Characteristics of an Immobilized Lipase for the Commercial Synthesis of Esters, J. Am. Oil Chem. Soc. 65:927–931 (1988).
Author information
Authors and Affiliations
Corresponding author
About this article
Cite this article
Rosu, R., Yasui, M., Iwasaki, Y. et al. Enzymatic synthesis of symmetrical 1,3-diacylglycerols by direct esterification of glycerol in solvent-free system. J Amer Oil Chem Soc 76, 839–843 (1999). https://doi.org/10.1007/s11746-999-0074-7
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/s11746-999-0074-7