Methyl ricinoleate

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. 

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). 

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). 

The GC-MS chromatogram obtained with the same substance after acid methanolysis and silylation is presented in Figure 10.10. The major compounds are fatty acid methyl esters corresponding to a mixture of an animal fat (attested by the presence of E15 0 and E17 0 with ante and iso isomers) and castor oil (attested by the presence of methyl ricinoleate E18 1,120H) [32]. Diterpenoid or triterpenoid resin components are not observed. 

Much work has been done on the incorporation of castor oil into polyurethane formulations, including flexible foams [64], rigid foams [65], and elastomers [66]. Castor oil derivatives have also been investigated, by the isolation of methyl ricinoleate from castor oil, in a fashion similar to that used for the preparation of biodiesel. The methyl ricinoleate is then transesterified to a synthetic triol, and the chain simultaneously extended by homo-polymerization to provide polyols of 1,000, 000 molecular weight. Polyurethane elastomers were then prepared by reaction with MDl. It was determined that lower hardness and tensile/elongation properties could be related to the formation of cyclization products that are common to polyester polyols, or could be due to monomer dehydration, which is a known side reaction of ricinoleic acid [67]. Both side reactions limit the growth of polyol molecular weight. 

METHYL RICINOLEATE (Table III) Propane (Lower phase point, 91.3)... 

Figure 4.7 Experimental set-up for interesterification between castor oil and methyl oleate to produce methyl ricinoleate.

Azelaic acid can be prepared by the oxidation of castor oil with nitric acid by the oxidation of ricinoleic acid with nitric acid and with alkaline permanganate by the oxidation of methyl oleate with alkaline permanganate by the ozonization of oleic acid and decomposition of the ozonide by the ozonization of methyl ricinoleate and decomposition of the ozonide by the action of carbon dioxide upon 1,7-heptamethylene magnesium bromide by the hydrolysis of i,7-di(yanoheptane. ... 

Dioctyl phthalate Butyl stearate Methyl ricinoleate... 

The enzymatic polymerization of methyl ricinoleate was performed using an immobilized lipase from Pseudomonas cepacia as catalyst. Reactions were conducted in bulk, with molecular sieves, at 80°C, for 7 days to give poly(ricinoleic acid) with Mw > 1 x 10s (Scheme 4.3) [32]. This result is generally uncharacteristic of other reports on related monomers given that lipase-catalyzed esterification of secondary hydroxyls proceeds slowly (see below) and ricinoleic acid purity to achieve such molecular weights must be very high. 

EINECS 205-392-9 Flexricin P-4 Flexricin P-4 Methyl 12-acetoxy-9-octadecenoate Methyl 12-acetoxyoleate Methyl acetyl ricinoleate Methyl 0-acetylricinoleate Methyl ricinoleate, acetate Methylester kyseliny acetyiricinolejove NSC 2398 9-Octadecenolc acid, 12-(acetyloxy)-, methyl ester 9-Octadecenoic acid, 12-(acetyloxy)-, methyl ester, (9Z.12R)- 9-Octadecenoic acid, 12-(ace loxy)-, methyl ester, (R-(Z))- (9CI) Ricinoleic acid, methyl ester, acetate Ricinoleic acid, methyl ester, acetate Methyl 12-acetoxy-9-octadecenoate. All purpose plasticizer, lubricant for vinyls and lacquers. Liquid mp = -16 d = 0.938 soluble in most organic solvents insoluble in water LDso (mus orl) = 34,900 mg/kg. CasChem. 

Reaction with a, (-unsaturated ketone. Attempted Baeyer-Villiger reaction of 1, readily available from methyl ricinoleate, with tn-chloroperbenzoic acid under usual conditions unexpectedly leads to the known furanoid fatty acid (3), although in only 25% yield. When the epoxidation is conducted under milder conditions, the expected epoxide (2) is obtained readily. When this epoxide is refluxed in chloroform containing trace amounts of hydrogen chloride, 3 is obtained in 80% yield. This reaction may be relevant to biosynthesis of natural furanoid fatty acids such as 3. ... 

Wilbur, J. 2007. Final report on the safety assessment of Ricinus communis (castor) seed oil, hydrogenated castor oil, glyceryl ricinoleate, glyceryl ricinoleate se, ricinoleic acid, potassium ricinoleate, sodium ricinoleate, zinc ricinoleate, cetyl ricinoleate, ethyl ricinoleate, glycol ricinoleate, isopropyl ricinoleate, methyl ricinoleate, and octyldodecyl ricinoleate. Int. f. Toxicol. 26(Suppl. 3) 31-77. 

Lie Ken Jie, M.S F., Syed-Rahmatullah, M.S.K., and Wong, K.P. (1992) Efficient Synthesis of Long-Chain Furanoid Fatty Ester Derivative from Methyl Ricinoleate, Nat. Prod. Lett. 1,93-98. 

Appropriate hydroxy epoxides are also converted to hydroxytetrahydrofurans and, indeed, in some eases, the hydroxy epoxide could not be isolated but passed di-reetly to the hydroxytetrahydrofuran. Methyl ricinoleate, epoxidized with 3-ehloroperoxybenzoie aeid, gave the expected cw-epoxide, which was converted by BF3, to a 10-hydroxy-9,12-tetrahydrofuran. Similar reaction with methyl isorici-noleate followed a different course, i.e., the expected 12,13-epoxide could not be isolated but was transformed directly to a mixture of diastereoisomeric 13-hydroxy-... 

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