Ricinolate

The name ricinoleic acid is used in commerce for the mixture of fatty acids obtained by hydrolysing castor oil, and its salts are called ricinoleates. 

Castor oil (qv) contains a predominance of ricinoleic acid which has an unusual stmcture inasmuch as a double bond is present in the 9 position while a hydroxyl group occurs in the 12 position. The biochemical origin of ricinoleic acid [141-22-0] in the castor seed arises from enzymatic hydroxylation of oleoyl-CoA in the presence of molecular oxygen. The unusual stmcture of ricinoleic acid affects the solubiUty and physical properties of castor oil. 

Castor Oil. Castor oil [8001-79-4] (qv) is the fixed oil from the seeds of Picinus communis Linne. Pale yellowish or almost colorless, it is a transparent viscid Hquid with a faint, mild odor and a bland taste followed by a slightly acrid and usually nauseating taste. Its specific gravity is between 0.945 and 0.965. Castor oil is soluble in alcohol, and miscible with anhydrous alcohol, glacial acetic acid, chloroform, and diethyl ether. It consists chiefly of the glycerides of ricinoleic acid [141 -22-0], and isoricinoleic acid [73891-08-4], found in the small intestine. The seed contains a highly... 

Castor oil is a cathartic only after Hpolysis in the small intestine Hberating ricinoleic acid. Ricinoleic acid inhibits the absorption of water and electrolytes. It is commonly used for preparation of the large bowel for diagnostic procedures. 

The starting amino acid for nylon-11 is produced from methyl ricinoleate [141 -24-2] which is obtained from castor oil (qv). The methyl ricinoleate is pyrolized to methyl 10-undecylenate [25339-67-7] and heptanal [111-71-7]. The unsaturated ester is hydroly2ed and then converted to the amino acid by hydrobromination, followed by ammoniation and acidification. The CO-amino acid product is a soft paste containing water, which is dried in the first step of the polymeri2ation process. 

Amide yields of up to 90—95% are reported from lauric acid and urea (1 1 mole ratio) by ramping the reaction temperature from 140 to 190°C over 4 hours. Oleic, stearic, linoleic, and ricinoleic acids gave similar results (19,20). The reaction does not form significant quantities of bisamides, but rehes on the decomposition of a substituted urea amide, releasing CO2 and NH. ... 

Sulfated Natural Oils and Fats. Sulfated natural triglycerides were the first nonsoap commercial surfactants introduced in the middle of the nineteenth century. Since then sulfates of many vegetable, animal, and fish oils have been investigated (see also Fats AND FATTY oils). With its hydroxyl group and a double bond, ricinoleic acid (12-hydroxy-9,10-octadecenoic acid) is an oil constituent particularly suited for sulfation. Its sulfate is known as turkey-red oil. Oleic acid is also suited for sulfation. Esters of these acids can be sulfated with a minimum of hydrolysis of the glyceride group. Polyunsaturated acids, with several double bonds, lead to dark-colored sulfation products. The reaction with sulfuric acid proceeds through either the hydroxyl or the double bond. The sulfuric acid half ester thus formed is neutralized with caustic soda ... 

PVB resins are also compatible with a limited number of plasticizers and resins. Plasticizers (qv) improve processibility, lower T, and increase flexibihty and resiUency over a broad temperature range. Usehil plasticizers include dibutyl and butyl benzyl phthalates, tricresyl and 2-ethylhexyl diphenyl phosphates, butyl ricinoleate, dibutyl sebacate, dihexyl adipate, triethylene glycol di-2-ethylbutyrate, tetraethylene glycol diheptanoate, castor oil, and others (64-73). 

Many substituted, ie, branched, fatty acids, particularly methacryUc, 2-ethylhexanoic, and ricinoleic acids, are commercially significant. Several substituted fatty acids exist naturally (Table 5). Fatty acids with a methyl group in the penultimate position are called iso acids, and those with a methyl group in the antepenultimate position are called anteiso acids (1) (see Carboxylic acids, branched-CHAIN acids). However, the term iso is often used in a broader sense to mean branched or mixtures of branched-chain industrial acids. 

Pyrolysis is used to produce undecenoic acid from ricinoleic acid ... 

Rhodium catalyst is used to convert linear alpha-olefins to heptanoic and pelargonic acids (see Carboxylic acids, manufacture). These acids can also be made from the ozonolysis of oleic acid, as done by the Henkel Corp. Emery Group, or by steam cracking methyl ricinoleate, a by-product of the manufacture of nylon-11, an Atochem process in France (4). Neoacids are derived from isobutylene and nonene (4) (see Carboxylic acids, trialkylacetic acids). 

Castor oil sulfation results largely in a sulfuric acid ester in which the hydroxyl group of ricinoleic acid has been esterified. However, other reactions can also take place. For example, the double bond can be attacked to produce an ester or the hydroxysulfonic acid (33). Hydrolysis of the sulfuric acid esters occurs during the reaction and subsequent treatment forming hydroxy acids and sulfuric acid. These hydroxy acids can be further sulfated. 

Alkali Fusion. Tha alkaU fusion of castor oil using sodium or potassium hydroxide in the presence of catalysts to spHt the ricinoleate molecule, results in two different products depending on reaction conditions (37,38). At lower (180—200°C) reaction temperatures using one mole of alkah, methylhexyl ketone and 10-hydroxydecanoic acid are prepared. The 10-hydroxydecanoic acid is formed in good yield when either castor oil or methyl ricinoleate [141-24-2] is fused in the presence of a high boiling unhindered primary or secondary alcohol such as 1- or 2-octanol. An increase to two moles of alkali/mole ricinoleate and a temperature of 250—275°C produces capryl alcohol [123-96-6] CgH gO, and sebacic acid [111-20-6] C QH gO, (39—41). Sebacic acid is used in the manufacture of nylon-6,10. 

The preparation of methyl 12-ketostearate from methyl ricinoleate has been accompHshed using copper chromite catalyst. The ketostearate can also be prepared from methyl ricinoleate in a two-step process using Raney nickel. The first step is a rapid hydrogenation to methyl 12-hydroxystearate, the hydrogen coming from the catalyst, followed by a slower dehydrogenation to product (50,51). 

Pyrolytic Decomposition. The pyrolytic decomposition at 350—460°C of castor oil or the methyl ester of ricinoleic acid spHts the ricinoleate molecule at the hydroxyl group forming heptaldehyde and undecylenic acids. Heptaldehyde, used in the manufacture of synthetic flavors and fragrances (see Elavors and spices Perfumes) may also be converted to heptanoic acid by various oxidation techniques and to heptyl alcohol by catalytic hydrogenation. When heptaldehyde reacts with benzaldehyde, amyl cinnamic aldehyde is produced (see Cinnamic acid, cinnamaldehyde, and cinnamyl... 

Polymerization of castor od, chemical or oxidative, results in higher viscosity or bodied ods that are more usehd in urethane coatings than the untreated castor od (87). Other castor derivatives used to prepare urethanes are amides prepared by reaction of castor od and alkanolamines, amides of ricinoleic acid with long-chain di- and triamines, and butanediol diricinoleate (88,89). 

Castor esters have been found to be nonirritating and noncomedogenic to the skin. Cetyl ricinoleate was found to be an effective noncomedogenic moisturizer (118). Castor-based quaternaries prepared by reaction of a castor fatty acid and a tertiary diamine are used for hair care. The ricinoleic quaternium is incorporated into clear shampoo formulations for foam enhancement and conditioning (119,120). 

Sebacic Acid. This acid is produced commercially by Union Camp in Dover, Ohio, by Hokoku OU Company in Japan, and by a state enterprise in the People s RepubHc of China (57). The process used in each case is based on the caustic oxidation of castor oU or ricinoleic acid [141-22-0] in... 

Ricinoleic acid (dl 12-hydroxyoleic acid) [14I-22-0J M 298.5, m 7-8° (a-form), 5.0° (7-form), n 1.4717, pKe, -4.5. Purified as methyl acetylricinoleate [Rider J Am Chem Soc 53 4130 1931], fractionally distilling at 180-185°/0.3mm, then 87g of this ester was refluxed with KOH (56g), water (25mL), and MeOH (250mL) for lOmin. The free acid was separated, crystd from acetone at -50°, and distd in small batches, b 180°/0.005mm. [Bailey et al. J Chem Soc 3027 1957.]... 

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