Fatty acids meadowfoam

Katengam S, Crane JM, Slabaugh MB, Knapp SJ (200J) Genetic mapping of a macromutation and quantitative trait loci underlying fatty acid composition differences in meadowfoam oil. Crop Sci 41 1927-1930... 

Cahoon, E.B. E.F. Marrillia K.L. Stecca S.E. Hall D.C. Taylor A.J. Kinney. Production of fatty acid components of meadowfoam oil in somatic soybean embryos. Plant Physiol 2000, 124, 243-251. 

Meadowfoam is composed of unique long-ehain fatty aeids with 5-eieosenoie acid (62%) as the major fatty aeid. The other main eomponents are 5,13-doeosa-dienoic acid (19%), 5-docosenoic acid (3%) and 13-docosenoic acid (10%). The A5 unsaturation provides an excellent chemical moiety for synthetic modifications to the oil or fatty acids by providing a site at which a carboxylate stabilized carbocation can form. In addition, the A5 unsaturation has enhanced resistance to oxidative degradation (8) as evidenced by the high OSI of the oil (246.9 h at 110°C) or its methyl ester (69.4 h at 90°C). 

One of the most important aspects of estolides is their demonstrated biodegradability (33). In addition, the oleic estolides and estolide esters show a great reduction in their pour points (pom points of-31 to -45°C) in comparison to their parent fatty acids or triglycerides. In contrast, meadowfoam estolides and the parent triglyceride... 

Lactones, due to their ring structure, are easily opened with nucleophiles (35) to yield the corresponding 5-hydroxy substituted derivatives (Scheme 12). Table 1 lists the relative rates of derivitization of meadowfoam fatty acids, y-lactones, and 8-lactones in reactions with alcohols and amines. All of the relative rates were compared with the rate of esterification for meadowfoam fatty acids (FA). These data clearly demonstrate the enhanced reactivity of the 8-lactone structure with respect to fatty acids and even its analog, y-lactone. 

Another aspect of the 8-lactone chemistry is the interconversion between 8-lac-tone and 5-hydroxy fatty acid. Under basic aqueous conditions, the equilibrium favors the formation of the 5-hydroxy fatty acids. In contrast, catalytic amounts of acid will cause rapid cyclization/dehydration of the 5-hydroxy fatty acid into the 8-lactone. By utilizing the equilibrium between these two species, 5-hydroxy fatty acids were synthesized directly from meadowfoam oil (Scheme 13). 

Other reported derivatives of meadowfoam include dimer acids and amides. Dimer acids were synthesized (40) from meadowfoam fatty acids at 250°C using montmorillonite clay as a catalyst with a yield of 44%. The physical properties (viscosity and lubricity) of the dimer acids were similar to those of other dimer acids prepared from highly monounsaturated fatty acids. Simple amides were also made by reaction of ammonia with fatty acids in refluxing xylenes (41). 

Isbell, T.A., and R. Kleiman, Mineral Acid-Catalyzed Condensation of Meadowfoam Fatty Acids into Estolides, J. Am. Oil Chem. Soc. 73 1097-1107 (1996). 

Frykman, H. B. and T.A. Isbell, Synthesis of 6-Hydroxy 8-Lactones and 5,6-Dihydroxy Eicosanoic/Docosanoic Acids from Meadowfoam Fatty Acids via Lipase-Mediated Self-Epoxidation, J. Am. Oil Chem. Soc. 74 719-722 (1997). 

For the last several years, there has been much interest in jojoba, Simmondsia chinensis, a plant native to the southwestern United States and Mexico, because of the presence of liquid wax esters in the seeds (Wisniak, 1988). Numerous schemes to convert desert land into orchards of these plants have been proposed. The oil is an excellent lubricant, has good emollient properties, and may replace sperm whale oil for many uses. As the fatty acid combination of Limnanthes douglasii (meadowfoam, Limnanthaceae) is quite similar to that of jojoba, the synthesis of a similar wax ester by hydrolysis and reduction followed by esterification has been proposed (Miwa and Wolff, 1962). 

Miwa, T. K. and I. A, Wolff, Fatty acids, fatty alcohols, and wax esters from Limnanthes douglasii (meadowfoam) seed oil, J. Am. Oil Chem. Soc., 39, 320-322 (1962). 

T.A. Isbell, Developmeta of meadowfoam as an industrial crop through novel fatty acid derivatives, Lipid Technology, 1997, 9, 140-144. T.A. Isbell, Lipid Synthesis and Manufacture (ed. F.D. Gunstone) Sheffield Academic Press, Sheffield (1999) pp.401-421. E.C. Leonard, Sources and commercial applications of high-erucic vegetable oils. Lipid Technology, 1994, 6, 79-83. 

For the selective epoxidation of specific fatty acids we expected to find such seed oils, containing cis-5-icosenoic (Eicosenoic) acid as the main component. On the base our examination we had chosen a plant with short life cycle, with good genetic flexibility, Limnanthes alba Benth (LIMNANTHACEAE) (Meadowfoam), which is native in North-America. It is well adapted to the our climate, and has good oil-yield (25.9%), with high concentration of icosenoic acid (46.8%) in total fatty acids. 

Long-chain fatty acids generally are undesirable for food and feed use, but have been in demand for production of lubricants and polymers (Nylon 1313), and as plasticizers. Potential sources include Crambe abyssinica oil containing over 60 percent C22 Limnanthes alba (Meadowfoam) oil with 95 percent C20 and C22 Lunaria annua oil wth 40 percent C22 and 20 percent C24 Selenia grandis oil with 58 percent C22 Leavenworthia alabamica oil with 50 percent C22 and Marshallia caespitosa oil with 44 percent C22. ... 

Tallow affords derivatives with a predominantly C16-C18 chain length for the shorter C10-C14 chain length derivatives coconut oil is the preferred material. As other oils have become available in quantity and competitive in pricing they too have been adopted by surfactant manufacturers. Today, tallow and coconut are joined by palm, rapeseed and soya bean oils as fatty acid feedstocks for nitrogen surfactants using the nitrile process [1, 2]. New oils on the horizon such as meadowfoam, crambe and lesquerella have yet to make any significant impact, while other oils remain unexplored [3]. 

Moser, B.R., Knothe, G., Cermak, S.C., 2010. Biodiesel from meadowfoam Linmanthes alba L.) seed oil oxidative stabdity and unusual fatty acid composition. Energy Environ. Sci. 3, 318-327. 

Interest in meadowfoam arose as part of a program to identify new, industrially useful crops for the U.S. farm economy (Miller et al., 1964 Higgins et al., 1971). Meadowfoam seed oil was found to have >90% of its fatty acids with a chain length of C20 or C22 (Miller et al., 1964) (Table 11.7.1). The main components of the Limnanthes alba oil were identified as d5-5-eicosenoic... 

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