Ricinoleic acid, in castor oil

The most abundant fatty acids in vegetable oils and fats are palmitic acid (hexa-decanoic acid or 16 0), oleic acid ([9Z]-octadec-9-enoic acid or 18 1 cis-9), and lino-leic acid (cis, cis-9,12-octadccadicnoic acid or 18 2 cis-9 cis-12) [21], Other fatty acids are found in special oils (e.g. 80% 87% ricinoleic acid in castor oil) [23], but these oils are quite rare. Castor oil, for example, has a production rate of 610,000 tons/year compared to the top four palm oil (46 million tons/year), soya oil (40 million tons/year), rapeseed oil (24 million tons/year), and sunflower oil (12 million tons/ year) [24]. Further sources of fatty acids are tall oils (2 million tons/year) [25] and to a lesser degree synthetic fatty acids derived by mainly hydroformylation and hy-drocarboxylation of olefins [23], The summed fatty acid production is estimated to be 8 million tons/year (2006) [23],... 

Tan, B.B., A.L. Noble, M.E. Roberts, J.T. Lear, and J.S.C. English. 1997. Allergic contact dermatitis from oleyl alcohol in lipstick cross-reacting with ricinoleic acid in castor oil and lanoUn. 

Castor oil is a natural polyol and its glyceryl esters consist of 90-95% ricinoleic acid and 5-10% oleic, linoleic and other fatty acids. Castor oil is approximately 80% trifunctional and 20% difunctional (the average hydroxyl functionality = 2.8 equivalent). Ricinoleic acid in castor oil is treated with ethylene glycol, diethylene glycol and triethylene glycol at 230°C to obtain a series of difunctional polyester polyols. ... 

Ricinoleic acid (i -12-hydroxy-9-cw-octadecenoic acid) (Fig. 6) accounts for 80-90% of fatty acids in castor oil (from Ricinus communis). It is found in other plant species and in the sclerotia of the ergot fungus Claviceps purpurea). Lesquerolic acid (i -14-hydroxy-ll-cw-eicosenoic acid), which is a C20 homolog of ricinoleic acid, occurs in Lesquerella species (up to 70% of total fatty acids). Isoricinoleic acid (i -9-hydroxy-12-cw-octadecenoic acid, or 9-OH 18 2 12c) is a major acid in the Wrightia species. In plants, several C16 and C18 mono, di, and trihydroxy fatty acids are stmctural components of cutin (a polyester constituent of plant cuticle). 

Candida strains convert ricinoleic acid into If-decalactone, which displays the fatty, fruity aroma typical of peaches. Ricinoleic acid (12-hydroxy octadec-9-enoic acid) is the major fatty acid in castor oil (approx. 80 %). The yeast can lipolyze castor oil glycerides and the liberated ricinoleic acid is subsequently metabolized via d-oxidation and eventually converted to 4-hydroxy-decanoic acid (Figure 5). Recently a European patent has been filed (20) essentially covering the same procedure. Shake culture fermentations were carried out on 100 ml scale for one week. The 4-hydroxydecanoic acid formed was converted to )f-decalactone by boiling the crude, acidified (pH 1.5) fermentation broth for a period of 10 minutes. The lactone was isolated via solvent extraction and a yield of some 5 g/1 was obtained. The same lactone was detected as the major volatile component formed when the yeast, Sporobolomyces odorus was grown in standard culture medium (21). Although the culture medium displayed an intense fruity, typical peach-like odor, the concentration of y-decalactone amounted to no more than 0.5 mg/1. 

The regiospecific characterization of TAG as lithiated adducts by collisionally activated dissociation tandem mass spectrometry (CAD-MS ) has been reported by Hsu and Turk [9]. The ions were reported from the loss of fatty acids as a,p-unsaturated fatty acid specific at the sn-2 position of TAG of lithiated adducts. We have used these ions to quantitate six regiospecific diricinoleoylacylglycerols (RRAcs) containing ricinoleate (a hydroxyl fatty acid) in castor oil [10],... 

One of our major areas of development was the synthesis and study of the chromatographic (8-10), spectroscopic (11-14), and spectrometric properties of a large number of heteroaromatic fatty acid derivatives (each containing either a furan, pyrrole, thiophene, selenophene, or tellurophene nucleus). These fatty acid derivatives were obtained by total synthesis or by partial synthesis from polyunsaturated unsaturated fatty acids (12,13,15-18) and unsaturated hydroxylated fatty acids, such as ricinoleic acid (from castor oil) (19-24). In this range of heteroaromatic fatty acid derivatives, only fatty acids containing a furan nucleus are found in nature (lipid extracts of the pike and salmon and from the latex of the rubber plant) (25-29). A typical method for the preparation of a disub-... 

Natural monohydroxy acids which are either saturated or contain non-conjugated unsaturation are listed in Table 1.8. Ricinoleic acid (12-hydroxyoleic) is the best known being the major acid in castor oil. Isoricinoleic acid is an isomer with the double bond and hydroxyl group interchanged. Densipolic acid is... 

Up until now, mostly pure substrates such as methyl oleate and its -isomer, methyl elaidate, have been tested as model substrates for hydroformylation, but in a few cases, linoleates, linolenates, and esters of ricinoleic acid have also been investigated (Figure 6.10). Oleic acid can be derived from new sunflower, linoleic acid from soybean, linolenic acid from linseed, and ricinoleic acid from castor oil. The long-chain mono-unsaturated fatty acid erucic acid (C22) can be extracted from old rapeseed oil. 

Sebacic acid is normally made from castor oil, which is essentially the triglyceride of ricinoleic acid. The castor oil is heated with sodium hydroxide at about 250" C. This treatment results in saponification of the castor oil to... 

Certain oiis contain characteristic fatty acids, such as ricinoleic acid in castor oii, with hydroxyoieic acid (12-hydroxy-9-octadecenoic acid) eieostearic acid in tung oil, with a conjugated triene licanic acid in oiticica oil, with a conjugated triene keto acid, which are responsibie for the high reactivity of the parent oils. 

Other examples of the direct use of ricinoleic or lesquerolic acid, or their TAG, have been reported. Polyesters of castor oil and succinic acid, a bio-refinery platform chemical, have potential utility in personal care products (O Lenick and LaVay, 2002). Copolymers of lactic acid and ricinoleic acid, and castor oil esterified to polylactic acid have utility in drug delivery systems (Sokolsky-Papkov et al., 2009). Thames and co-workers prepared alkyds containing lesquereolic acid-trimethylolethane monoester and phthahc acid as comonomers through performing glycerolysis of lesquereUa oil, followed by the addition of phthalic anhydride, with the resultant material used in the preparation of polyurethanes (Thames et al., 1994). 

One species of Euphorbia in Brazil (Bernardia pulchelld) has been determined to contain more than 90% vemolic acid in the triglyceride [120]. This level of single-component purity is equivalent to the level of ricinoleic acid typically found in castor oil. These different varieties of epoxidized oil plants will probably continue to be the subject of agricultural development in the coming years. 

Ricinoleic acid (Figure 3.8) is the major fatty acid found in castor oil from seeds of the castor oil plant (Ricinus communis Euphorbiaceae), and is the 12-hydroxy derivative of oleic acid. It is formed by direct hydroxylation of oleic acid (usually esterified as part of a phospholipid) by the action of an 02- and NADPH-dependent mixed function oxidase, but this is not of the cytochrome P-450 type. Castor oil has a long history of use as a domestic purgative, but it is now mainly employed as a cream base. Undecenoic acid (A9-undecenoic acid) can be obtained from ricinoleic acid by thermal degradation, and as the zinc salt or in ester form is used in fungistatic preparations. 

A commercial castor oil (Delaware-Brazil) was used as purchased without any pretreatment. The fatty acid composition was determined using a gas chromatograph (HP 5890) with a flame ionization detector. The following instrumentation and conditions were used H2 as carrier gas, modified polyethylene glycol column (FFAP 2 - 25 m x 0.20 mm id x 0.30-mm film), column temperature of 180-210°C (2°C/min), injector temperature of 250°C, and detector temperature of 280°C. Using this procedure, the approximate fatty acid composition in castor oil is 92 wt% ricinoleic acid and 8 wt% other acids. Ethyl alcohol (95 v/v%) (Merck) and n-hexane PA (Merck) were used as substrate and solvent, respectively. 

Other Cig-fatty acids have also a high potential in hydroformylation, such as ricinoleic acid, which contains an additional hydroxy group at position 12 of the fatty carbon chain and which is not food relevant [26], The hydroformylation of ethyl ricinoleate, derived from castor oil, shows selectivity for cyclization of the carbon chain because of the reaction of the hydroxyl group with the formyl group (Scheme 8). 

Polyglycerol Polyricinoleic Acid is prepared by esterification of polyglycerol with condensed castor oil fatty acids. The castor oil fatty acids are mainly composed of 80% to 90% ricinoleic acid. It is a clear, light brown, viscous liquid. It is soluble in ether, in hydrocarbons, and in halogenated hydrocarbons. It is insoluble in water and in alcohol. 

Large supply of naturally derived lipids can be obtained from plants in which many oils and fatty acids can be readily extracted and purified. Animal sources (e.g., eggs or milkfats) are used to derive complex lipids such as phospholipids and cholesterol. Yield from natural sources is dependent on the weight-percent composition and the efficiency of the extraction procedure. The constitution of fatty acids in vegetable oils varies widely from different sources. For example, oleic acid is present at 64.6% by weight in olive oil but is present at only 0.7% in palm kernel oil. Similarly, castor oil triglyceride is comprised of almost entirely ricinoleic chains. There are numerous raw material suppliers of oils and oil fractions worldwide. As such, the relative cost of bulk purified... 

Traditional fermentation using microbial activity is commonly used for the production of nonvolatile flavor compounds such as acidulants, amino acids, and nucleotides. The formation of volatile flavor compounds via microbial fermentation on an industrial scale is still in its infancy. Although more than 100 aroma compounds may be generated microbially, only a few of them are produced on an industrial scale. The reason is probably due to the transformation efficiency, cost of the processes used, and our ignorance to their biosynthetic pathways. Nevertheless, the exploitation of microbial production of food flavors has proved to be successful in some cases. For example, the production of y-decalactone by microbial biosynthetic pathways lead to a price decrease from 20,000/kg to l,200/kg U.S. Generally, the production of lactone could be performed from a precursor of hydroxy fatty acids, followed by p-oxidation from yeast bioconversion (Benedetti et al., 2001). Most of the hydroxy fatty acids are found in very small amounts in natural sources, and the only inexpensive natural precursor is ricinoleic acid, the major fatty acid of castor oil. Due to the few natural sources of these fatty acid precursors, the most common processes have been developed from fatty acids by microbial biotransformation (Hou, 1995). Another way to obtain hydroxy fatty acid is from the action of LOX. However, there has been only limited research on using LOX to produce lactone (Gill and Valivety, 1997). 

A Flavobacterium sp. can be used to hydrate linoleic acid to 10-hydroxy-12(2)octadecenoic acid, an analogue of ricinoleic acid.222 Ricinoleic acid (12-hydroxy-9(.Z)oc-tadecenoic acid) from castor oil is important in the preparation of paints and varnishes.223 Cryptococcus neofor-mans can convert /3-pentadecane to the corresponding a-cu-dicarboxylic acid (HOOC(CH2)i3COOH).224 Toluene can be converted to 4-hydroxybenzoic acid... 

Other modifications of vegetable oils in polymer chemistry include the introduction of alkenyl functions, the study of novel polyesters and polyethers and the synthesis of semi-interpenetrating networks based on castor oil (the triglyceride of ricinoleic acid) [42], and also the production of sebacic acid and 10-undecenoic acid from castor oil [44]. Additionally, the recent application of metathesis reactions to unsaturated fatty acids has opened a novel avenue of exploitation leading to a variety of interesting monomers and polymers, including aliphatic polyesters and polyamides previously derived from petrochemical sources [42, 45]. 

Fig. 2. The Cl 8 high-performance liquid chromatography (HPLC) radiochromatogram (B) for the separation of molecular species of acylglycerol (AG) in the AG fraction (see Fig. 1, 5 from 100 il methanol solution) from the castor microsomal incubation (60 min) of [ " C]-ricinoleic acid co-chromatographed with castor oil. (For HPLC conditions, see Experimental Procedures.) The upper ultraviolet (UV 205 nm) chromatogram (A) shows the separation of molecular species of AG in castor oil.

Hydroxy fatty acids are formed as intermediates in various metabolic sequences (e.g. fatty acid biosynthesis, -oxidation) and also as a result of specific hydroxylation reactions. The hydroxyl group is usually introduced close to one end of the acyl chain (e.g. a-,co-) and less commonly in the middle of the chain. A good example of the latter in plants is the formation of ricinoleic acid (the major acid of castor oil. Section 3.3.4) by hydroxylation of oleoylphosphatidylcholine substrate using NADH and oxygen as cofactors (Moreau and Stumpf, 1981). 

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