Quantitation of estolide triglycerides in sapium seeds by high performance liquid chromatography with infrared detection

Payne-Wahl, Kathleen; Kleiman, R.

doi:10.1007/bf02660218

Cited by 23 publications

(8 citation statements)

References 6 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Recent interest in the utilization of the invasive shrub Sapium sebiferum (Chinese tallow) may provide a source for an allenic estolide, 8-(2(E), 4(Z)-decadienoyl)-5(E), 6-(E)-octadecadienoic acid, (Aitzetmuller et. al., 1992;Payne-Wahl and Kleiman 1983). The last member of this unique group of seed oils are the estolides derived from lesquerella auriculata.…”

Section: Chemistry and Physical Properties Of Estolidesmentioning

confidence: 99%

Chemistry and physical properties of estolides

Isbell¹

2011

Grasas y Aceites

View full text Add to dashboard Cite

show abstract

Section: Chemistry and Physical Properties Of Estolidesmentioning

confidence: 99%

Chemistry and physical properties of estolides

Isbell¹

2011

Grasas y Aceites

View full text Add to dashboard Cite

show abstract

“…Estolides have been found in nature (6,7) and have been synthesized (1)(2)(3)(4)8) in the laboratory. Isbell and Kleiman (9) synthesized estolides from oleic fatty acids and found them to have interesting chemical behavior.…”

mentioning

confidence: 99%

Synthesis of estolides from oleic and saturated fatty acids

Cermak

Isbell

2001

J Americ Oil Chem Soc

View full text Add to dashboard Cite

Oleic acid and various saturated fatty acids, butyric through stearic, were treated with 0.4 equivalents of perchloric acid at either 45 or 55°C to produce complex estolides. Yields varied between 45 and 65% after Kugelrohr distillation. The estolide number (EN), i.e., the average number of fatty acid units added to a base fatty acid, varied as a function of temperature and saturated fatty acid. The shorter-chain saturated fatty acids, i.e., butyric and hexanoic, provided material with higher degrees of oligomerization (EN = 3.31) than stearic acid (EN = 1.36). The individual, saturated fatty acid estolides each have very different characteristics, such as color and type of by-products. The higher-temperature reactions occurred at faster rates at the expense of yield, and lactones were the predominant side products. At 55°C, lactone yields increased, but the δ-γ-lactone ratio decreased; this led to lower estolide yields. The opposite trend was observed for the 45°C reaction. The saturate-capped, oleic estolides were then esterified with 2-ethylhexyl alcohol, and the chemical composition of these new estolides remained consistent throughout the course of the reaction.Paper no. J9799 in JAOCS 78, 557-565 (June 2001).Estolides are a class of esters, based on vegetable oils (1-4), that form when the carboxylic acid functionality of one fatty acid reacts at the site of unsaturation of another fatty acid to form an ester linkage. These linkages are used to help characterize the structure of the estolide since the estolide number (EN) is defined as the average number of fatty acids added to a base fatty acid (Scheme 1, EN = n + 1). The secondary ester linkages of the estolide are more resistant to hydrolysis than those of triglycerides, and the unique structure of the estolide results in materials that have far superior physical properties for certain applications than vegetable and mineral oils (5). Estolides have been found in nature (6,7) and have been synthesized (1-4,8) in the laboratory. Isbell and Kleiman (9) synthesized estolides from oleic fatty acids and found them to have interesting chemical behavior. The double bond in oleic acid is located at the 9 position which, under the correct conditions of acid concentration, reaction time, and temperature, undergoes estolide formation with minimal migration. The proposed mechanism involves formation of a carbocation that can undergo nucleophilic addition with or without carbocation migration along the length of the chain. If the migration continues to the C4 and C5 position, the fatty acid will cyclize to form lactones, the major side product to estolide formation (Scheme 2) (10-15).Lactones are formed from an intramolecular cyclization of a fatty acid carboxyl group with a carbocation located at the 4-or 5-position on a fatty acid backbone. Under the correct conditions, Showell et al. (13) and Cermak and Isbell (14,15) were able to produce γ-and δ-lactones, respectively. A major side product in the estolide synthesis, lactones are an interesting class of compounds...

show abstract

“…Estolides (shown in Scheme 1) are formed when the carboxylic acid group of one fatty acid forms an ester bond with either a hydroxyl group or a double bond on the carbon chain of a second fatty acid (1)(2)(3)(4). They can be produced by changing the reaction conditions of dimerization reactions (5,6)…”

mentioning

confidence: 99%

Quantitation of estolides by Fourier transform infrared spectroscopy

Erhan

Kleiman

Abbott

1996

J Americ Oil Chem Soc

Self Cite

View full text Add to dashboard Cite

Estolides were produced from meadowfoam oil fatty acids, oleic, linoleic, petroselinic, and cis-5,cis-13 docosadienoic acids. Estolide reaction mixtures were quantitated by Fourier transform infrared spectroscopy and compared to the area percentages determined by high-performance liquid chromatography. The absorbance frequency of estolide carbonyl (I 737 cm -I) is different than the [actone carbonyl (I 790 cm -I) and the acid carbonyl (I 712 cm -I). Estolide standards were obtained by wiped-film molecular-still distillations and column chromatography. JAOCS 73, 563-567 (1996).Estolides have potential uses in lubricants, greases, plasticizers, printing inks, and cosmetics. An accurate method of analysis will enable the reaction to be closely monitored and to make changes at desired times to shift the delicate esterification balance in favor of the desired products. Fourier transform infrared spectroscopy (FTIR) spectrometers are useful tools for this purpose because they have high signal-to-noise ratios, extensive data manipulation capabilities, such as subtraction and deconvolution of spectra, and can be used for continuous on-line monitoring of industrial processes (7). KEY WORDS: Estolide, FTIR, meadowfoam oil fatty acids, vegetable oil fatty acids.

show abstract

Quantitation of estolide triglycerides in sapium seeds by high performance liquid chromatography with infrared detection

Cited by 23 publications

References 6 publications

Chemistry and physical properties of estolides

Chemistry and physical properties of estolides

Synthesis of estolides from oleic and saturated fatty acids

Quantitation of estolides by Fourier transform infrared spectroscopy

Contact Info

Product

Resources

About