Estolides

Two of the three attractant pheromones identified to date are very close structurally to those used in primary metabolism. The biosynthesis of the estolide 5 probably starts from 3-hydroxybutyric acid (4), an intermediate in fatty acid biosynthesis (Fig. 4.3). Condensation of two units furnishes the pheromone 5. The formation of cupilure (3 Fig. 4.2) can be easily explained by two methylations from ubiquitous citric acid. Both compounds are unlike any known insect pheromones, whereas the third known attractant pheromone (ketone 1 Fig. 4.1), bears some resemblance to some insect pheromones. A proper comparison of the differences and similarities between insect and arachnid pheromones will require the identification of representative compounds from most of the families of both groups of organisms. 

Wool (anhydrous lanolin) 36-42 Cholesteryl estolidic esters, alcohol esters of iso- and anteiso acids... 

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... 

Lawate, S.S., Triglyceride Oils Thickened with Estolides of Hydroxy-Containing Triglycerides, U.S. Patent 5,427,704 (1995). 

Isbell, T. A., R. Kleiman, and B.A. Planner, Acid-Catalyzed Condensation of Oleic Acid into Estolides and Polyestolides, J. Am. Oil Chem. Soc. 71 169-174 (1994). 

D hydroxy esters or estolides by cleavage with fatty acids from high-oleic sun-... 

H2O2 yields of epoxide varied from 0 to 91% (57). Formation of dihydroxy acids or estolides did not occur. The lipase was still active after 15 uses. Forty carboxylic acids were used as substrates for the lipase-catalyzed formation of peracids (58). Good agreement between the amount of peracid formed and epoxidation of 1-octene was obtained. Neither a-substituted carboxylic acids nor aromatic acids was converted to peracids. 

Ng, S., and Jaworski, J.G. (2010) The cytochrome P450 GYP85A22 is a fatty acyl-GoA omega-hydroxylase essential for Estolide synthesis in the stigma of Petunia hybrida. J. Biol Chem., 285, 3985-3996. 

Stillingia oil, the kernel oil, is unusual in that it contains significant amounts of deca-2,4-dienoic acid (8-10%) and the optically active allenic acid 8-hydroxy octa-2,3-dienoic acid (8-10%) (Sprecher a/., 1965 Christie, 1969). These short-chain acids are present as a Ci8 estolide which can be separated by chromatography (Payne-Wahl and Kleiman, 1983). (Sections 1.5,1.6,1.9,3.2.10 and 3.2.15). 

Limnanthes alba) fatty acids into estolides. The ester linkages were found to be mainly in the original double bond positions, but some positional isomerization was also observed. 

Dehydration of a suitable precursor at high temperature under vacuo initially yielded a polyester (8), upon which pyrolysis afforded the trans-9,trans-11-18 2 isomer. For this procedure ricinoleic acid was first elaidinized, which means a transformation of the ds- double bond into a trans- double bond (9). The so formed ricinelaidic acid was then heated under vacuum at 235°C. Intermolecular esterification (estolide formation) yielded polyesters with a molecular weight of 1500 to 1600. Pyrolysis and simultaneous distillation furnished a crude product, which was recrystallized in 95% ethanol to furnish the desired trans-9,trans-W- % 2 isomer in a 35% yield. 

Martin-Arjol, I Busquets, M Manresa, A. Production of 10(S)-hydroxy-8(E)-octadecenoic acid mono-estolides by lipases in non-aqueous media. Process Biochemistry, 2013, v. 48 (2), 224-230. 

With the aid of adsorption TLC, it has been discovered that the seed oil of the Chinese tallow tree (Sapium sebiferum) contains up to about 25% of a fraction only a little more polar than normal triglycerides. These compounds have been characterised as mono-estolide triglycerides, i. e. (mono)hydroxy-triglycerides, esterified with ordinary fatty acids [192]. The following types of estolide-triglyceride have been... 

The mono-, di- and tri-estolide triglycerides were isolated by TLC the fatty acid components of each fraction were determined gas chromato-graphically [141]. 

A Cg hydroxy allenic acid (8-OH 2,3-8 2 stillingic) is present in stillingia oil (8-10%) where it is associated with 2f4c-10 2 to make a C,g estolide. Many Cjj allenic acids have been synthesised. 

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