Synthesis of Chloroalkoxy eicosanoic and docosanoic acids from meadowfoam fatty acids by oxidation with aqueous sodium hypochlorite

Mund, Melissa S.; Isbell, Terry A.

doi:10.1007/bf03028872

Cited by 3 publications

(4 citation statements)

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“…Initial work to synthesize a chloro alkoxy compound from methyl oleate utilized a bleach and acetic acid extraction procedure reported by Mund and Isbell [3]. Using the Mund and Isbell conditions, methanol and methyl oleate produced the two desired methyl 9-chloro-10-methoxyoctadecanoate and methyl 10-chloro-9-methoxy-octadecanoate positional isomers (chloro methoxy), as well as chlorohydrin, dichloro, and chloro acetate products.…”

Section: Resultsmentioning

confidence: 99%

“…A difunctional chloro alkoxy material can be made through the reaction of the olefin with hypochlorous acid and alcohol ( Fig. 1) [3]. The final product is a mixture of positional isomers (9-chloro-10-alkoxy and 9-alkoxy-10-chloro-) with the chlorine adjacent to the alkoxy substituent.…”

Section: Introductionmentioning

confidence: 99%

“…Hypochlorous acid generated in situ was used in this study due to its low cost, ease of handling, and potential to scale up. Numerous alcohol nucleophiles will participate in the formation of the chloro alkoxy compounds as well [3,6].…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of Chloro Alkoxy and Alkoxy Derivatives of Methyl Oleate

Lowery

Andersh²,

Isbell

2013

J Americ Oil Chem Soc

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Vegetable oil based lubricants typically have improved lubricity and biodegradability over their mineral oil based counterparts. However, vegetable oil lubricants often fail to meet the performance standards of mineral based oils with respect to cold temperature and resistance to oxidation. Olefins are an oxidatively weak point for vegetable based compounds. Removal of the olefin in a vegetable based lubricant through functionalization may increase resistance to oxidation. If the added functionality also causes branching of the alkyl chain, cold temperature properties may be improved. Any chemical modifications considered must be scalable and cost-effective to be useful in a commercial application. In this study, methyl oleate was functionalized into a chloro alkoxy derivative. Sodium hypochlorite (household bleach) and calcium hypochlorite were both used to generate hypochlorous acid in situ. Hypochlorous acid and a series of alcohols (methanol, ethanol, and butanol) were reacted with methyl oleate to make chloro alkoxy compounds in 29.8-77.9 % yields. In an effort to make a branched saturated ether we removed the chlorine moiety of the chloro alkoxy compounds. Dehalogenation was achieved under basic conditions over a Pd/C catalyst in 2-propanol. Reaction times increased substantially as the size of the adjacent alkoxy group increased. The reaction rate could be improved by heating the reactions above 100°C in a pressure reactor. Increased reaction temperature also resulted in an increase in ketone side products from the competing elimination reactions. Saturated ether yields were 4.1-43.2 %.Names are necessary to report factually on available data; however, the USDA neither guarantees nor warrants the standard of the product, and the use of the name by USDA implies no approval of the product to the exclusion of others that may also be suitable.Electronic supplementary material The online version of this article (

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Synthesis of Chloro Alkoxy and Alkoxy Derivatives of Methyl Oleate

Lowery

Andersh²,

Isbell

2013

J Americ Oil Chem Soc

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“…The principal fatty acids of meadowfoam oil are erucic acid, cis ‐5‐eicosenoic acid (20:1Δ5), cis ‐5‐docosenoic acid (22:1Δ5), and cis ‐5, cis ‐13‐eicosenoic acid (22:2Δ5Δ13) or dienoic acid (Earle et al, 1959; Smith et al, 1960; Bagby et al, 1961). The unique functionality of meadowfoam oil can be partly attributed to the presence and high concentration of Δ5 double bonds (Erhan et al, 1993; Isbell, 1997; Isbell et al, 1999; Isbell, 1999; Mund and Isbell, 1999). The mean concentration of Δ5 unsaturated fatty acids among L alba germplasm accessions is 830 g kg −1 (Knapp and Crane, 1995).…”

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Genetic Mapping of a Macromutation and Quantitative Trait Loci underlying Fatty Acid Composition Differences in Meadowfoam Oil

et al. 2001

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The seed oil of meadowfoam (Limnanthes alba Hartw. ex Benth.) is a rich source of very long‐chain fatty acids (VLCs), primarily 20:1Δ5, 22:1Δ5, 22:1Δ13 (erucic acid), and 22:2Δ5Δ13 (dienoic acid). Wild‐type L alba ssp. versicolor populations produce more erucic and less dienoic acid than wild‐type L. alba ssp. alba populations, phenotypic differences that are caused by the macromutation E and possibly by quantitative trait loci (QTL). The aim of this study was to map the E locus and QTL affecting fatty acid concentrations among intersubspecific backcross progeny. The segregation ratio for the E locus (94 Ee to 86 ee progeny) was not significantly different from one to one (P = 0.84). The E locus was associated with 94 and 77% of the phenotypic variance for erucic and dienoic acid concentration, respectively. Erucic acid varied from 42 to 151 g kg−1 among Ee and 185 to 269 g kg−1 among ee progeny, while dienoic acid varied from 151 to 318 g kg−1 among Ee and 66 to 209 g kg−1 among ee progeny. The E locus mapped to Linkage Group 4 and pleiotropically affected every VLC. Composite interval mapping, performed with the E locus and 18 background markers as cofactors, was used to search the genome for QTL. Two significant QTL peaks were found for erucic and dienoic acid on Linkage Group 4. One QTL was centered on the E locus and produced a massive peak. The other QTL produced a marginally significant peak 30.4 cM downstream of the E locus and was associated with less than 1% of the phenotypic variance. The segregation of additional QTL in this population affecting dienoic acid cannot be ruled out.

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Enzyme‐Catalyzed modification of oilseed materials to produce eco‐friendly products

Hayes

2004

J Americ Oil Chem Soc

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Novel products produced from seed oil materials (TAG, phospholipids, and minor components such as tocopherols, sterols, stanols, and fatty acyl esters of the latter two) by enzyme-mediated purification or chemical modification are reviewed. The primary focus is on "value-added products" of current and potential use (particularly in the food, cosmetics, and pharmaceutical industries) that require the selectivity of enzymes and mild operating conditions, the latter being beneficial for polyunsaturated and oxygenated acyl groups. The paper briefly reviews the biochemistry of enzymes in lipid modification (lipases, phospholipases, and lipoxygenases) and discusses and assesses the current and future applications, current state of the art, and areas for future research for the following enzyme-mediated processes: isolation of polyunsaturated and oxygenated FFA; formation of structured TAG as nutraceuticals; formation of MAG, saccharide-FA esters, and other polyhydric alcohol ester as emulsifiers and surfactants; isolation and/or modification of tocopherols and sterols as antioxidants; formation of hydroperoxides as chemical intermediates; and modification of phospholipids for use in liposomes.Agriculturally derived feedstocks will play an increasingly important role in North America and worldwide as the cost of petroleum continues to increase and its availability decreases. Lipids (TAG, phospholipids, sterols, etc.) are an example of such a feedstock. Although lipids are readily modified by chemical means (reviewed in Refs. 1-5) and can be synthesized from petroleum-based feedstocks (6), there is an increased interest in modifying lipids via biocatalysis, particularly to manufacture lipid-based products in the food, cosmetics, and pharmaceutical industries, and for applications focused on environmental friendliness, due to the mild reaction conditions and narrow product distributions. In addition, biocatalysis has also played a role in isolating natural products, for instance, by temporarily modifying the molecule of interest to facilitate downstream separations. Reviews on biocatalytic modification of lipids have appeared during the last 15 yr (7-11) and more recently in two monographs (12,13). In addition, a recent conference entitled Enzymes in Lipid Modification was held in 2003 in Greifswald, Germany (14). The organization and emphasis of the previous reviews focused mostly on the types of biocatalysts; the emphasis here is on the products formed. Preceding the discussion of products is a brief overview of the important biocatalytic tools to be used. BIOCATALYSTS USED FOR LIPID MODIFICATIONLipases (EC 3.1.1.3). Lipases are specifically designed by nature for the hydrolysis and synthesis of ester bonds involving FA, and can form and/or hydrolyze amide, carbonate, and thioester bonds as well. Reactions catalyzed by lipases that involve the ester bond are diagrammed in Figure 1. Lipases are perhaps the most frequently used enzymes for biotransformations because of their ability to function in nonaqueous and aqueous ...

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Synthesis of Chloroalkoxy eicosanoic and docosanoic acids from meadowfoam fatty acids by oxidation with aqueous sodium hypochlorite

Cited by 3 publications

References 19 publications

Synthesis of Chloro Alkoxy and Alkoxy Derivatives of Methyl Oleate

Synthesis of Chloro Alkoxy and Alkoxy Derivatives of Methyl Oleate

Genetic Mapping of a Macromutation and Quantitative Trait Loci underlying Fatty Acid Composition Differences in Meadowfoam Oil

Enzyme‐Catalyzed modification of oilseed materials to produce eco‐friendly products

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