Fatty methyl oleate

A similar reaction occurs with fatty acids (such as stearic acid) or methyl stearate, which undergo isomerization, cracking, dimerization, and oligomerization reactions. This has been used to convert solid stearic acid into the more valuable liquid isostearic acid [102] (Scheme 5.1-70). The isomerization and dimerization of oleic acid and methyl oleate have also been found to occur in chloroaluminate(III) ionic liquids [103]. 

The addition of an ester sulfonate of an unsaturated fatty acid improves the rinsing properties in washing tests. A mixture of 50% sodium methyl a-sulfostearate and 50% sodium salt of sulfonated methyl oleate (30 70 mono-sulfonate/polysulfonate ratio) was used [83]. 

C12 to C20, primarily Ci6 to ( is), used as surface lubricants in the manufacture of food-contact articles. The method, which uses ethyl palmitate (Eastman Chemicals No. 1575 Red Label) as an internal standard, has been validated at 200 ppm total FAME [185]. Other FAME standards (methyl palmitate, methyl stearate, methyl oleate, methyl linoleate and methyl linolenate) are available (Applied Science Laboratories) [116], Worked out examples of additive determinations are given in the Food Additives Analytical Manual [116], which also describes a great many of indirect food additives, such as BHA, BHT, TBHQ, l-chloro-2-propanol, DLTDP, fatty acid methyl esters, w-heptyl-p-hydroxybenzoate, propyl-gallate, sodium benzoate, sodium stearoyl-2-lactylate, sorbitol and phenolic antioxidants. EPA methods 606 and 8060 describe the CGC separation of phthalate esters (direct injection) (cf. Figure 4.2). 

Polymers Catalytic reactions involving C=C bonds are widely used for the conversion of unsaturated fatty compounds to prepare useful monomers for polymer synthesis. Catalytic C-C coupling reactions of unsaturated fatty compounds have been reviewed by Biermann and Metzger [51]. Metathesis reactions involving unsaturated fatty compounds to prepare co-unsaturated fatty acid esters have been applied by Warwel et al. [52], Ethenolysis of methyl oleate catalyzed by ruthenium carbenes developed by Grubb yields 1-decene and methyl 9-decenoate (Scheme 3.6), which can be very useful to prepare monomers for polyolefins, polyesters, polyethers and polyamide such as Nylon 11. 

The ability of titanium-grafted silicas in catalyzing the epoxidation with TBHP of fatty compounds was first tested on two pure Qg monounsaturated FAMEs methyl oleate (ds-9-octadecenoate Scheme 12.1) and methyl elaidate (trans-9-octadecenoate) [49]. In both cases, selectivity to 9,10-epoxystearate was very high (>95%) and the reaction was fully stereospecific, confirming that epoxidation with titanium catalysts and TBHP proceeds via a non-radical mechanism with retention of configuration at the C=C bond. Ti-MCM-41 was more active than Ti-SiC>2 (Fig. 12.1). Actually, methyl oleate was almost completely converted after... 

Fig. 12.1 Conversion of fatty acid methyl esters (FAMEs) methyl oleate ( ) and methyl elaidate ( ) vs. reaction time over Ti-MCM-41 (a) and overTi-Si02 (b). (Adapted from [49]).

Methyl linoleate, methyl oleate from methyl linoleate, methyl oleate, methyl esters of saturated fatty acids KY Toluene [184]... 

It is now well established (6,10) that the hydrocarbons, except possibly those having three or four carbon atoms, found in the irradiated meats can come only from the lipid. This hypothesis has been verified in earlier studies, when the volatiles from irradiated methyl oleate (10) were found to contain appreciable quantities of alkanes and alkenes, and now in more detail from studies of both triglycerides and fatty acid esters. 

Bond cleavage would be expected to lead to a homologous series of alkanes, alkenes, and esters to Cio if the fatty acid were oleate, but it would give higher homologs if the fatty acid were stearate. The principal products are, in fact, alkanes, alkenes, and a homologous series of methyl esters. The highest member of the alkane series found in irradiated methyl oleate... 

Fatty acid esters Ethyl acetate, methyl methacrylate, trimethylolpropane trimethacrylate, decyl methacrylate, 2-hydroxyethyl methacrylate, ethoxy ethyl acetate, methyl palmitate, ethyl palmitate, isopropyl palmitate, butyl palmitate, isobutyl palmitate, methyl margarate, butyl margarate, methyl stearate, ethyl stearate, butyl stearate, isobutyl stearate, methyl oleate, bis(2-ethylhexyl) adipate, bis(2-ethylhexyl) sebacate, methyl linoleate, methyl laurate, octyl laurate, methyl myristate, isobutyl myristate, butyl myristate, dihydroisopimaric add methyl ester... 

The application of olefin metathesis to fatty acids and related compounds has its starting point in 1972 with the selective transformation of methyl oleate into equimolar amounts of 9-octadecene and dimethyl 9-octadecene-l,18-dioate by Van Dam, Mittelmeijer, and Boelhouwer (Scheme 1) [29]. In this early work, 1-2 mol% of a... 

Scheme 3 Access to fatty ester derivatives via CM of methyl oleate with ethylene (ethenolysis), nonfunctional olefins, and functional olefins...

The production of a,m-diesters from fatty esters can be realized via their SM as already explained, but it can also be performed by CM with methyl acrylate. The bulk CM of several unsaturated fatty acid methyl esters containing double bonds in different positions with methyl acrylate was studied by Rybak and Meier (Scheme 6) [43], C4 and C5 displayed very good activities with high conversions and CM selectivities. Among them, C5 showed the best performance for both methyl oleate (97% conversion, 92% selectivity, with 0.2 mol%) and methyl 10-undecenoate (99% conversion, 99% selectivity, with 0.1 mol%). The same conditions were successfully applied to methyl erucate and methyl petroselinate. The reaction conditions were further optimized, also considering the effect of 1,4-benzoquinone as additive for the reduction of double-bond isomerization [39], The CM of methyl 10-undecenoate and methyl acrylate worked with full conversions and high selectivity if five- to tenfold excess of methyl acrylate is used. Furthermore, using a 1 1 ratio between both reactants led, after optimization of the reaction... 

The ene-yne CM of fatty acid-derived terminal alkenes with several alkyne derivatives was shown by Bruneau et al. [75], These reactions, which led to renewable conjugated dienes, were performed in a one-pot two-step procedure. In the first step, the ethenolysis of methyl oleate was performed in the presence of the first-generation Hoveyda-Grubbs catalyst (2.5 mol%) using dimethyl carbonate as solvent at room temperature. After completion of the ethenolysis (90% conversion), C4 (1 mol%) and the corresponding alkyne (0.5 equivalents with respect to olefins) were added and the reaction was run at 40°C for 2 h (Scheme 9). The desired dienes were thus obtained in high yields close to the maximum theoretical value (50%). Moreover, in order to maximize the formation of functional dienes, the same reaction sequence was applied to the diester obtained by SM of methyl oleate. In this way, the yield of functional dienes was increased up to 90% depending on the... 

Ferulic acid, a phenolic acid that can be found in rapeseed cake, has been used in the synthesis of monomers for ADMET homo- and copolymerization with fatty acid-based a,co-dienes [139]. Homopolymerizations were performed in the presence of several ruthenium-based olefin metathesis catalysts (1 mol% and 80°C), although only C5, the Zhan catalyst, and catalyst M5i of the company Umicore were able to produce oligomers with Tgs around 7°C. The comonomers were prepared by epoxidation of methyl oleate and erucate followed by simultaneous ring opening and transesterification with allyl alcohol. Best results for the copolymerizations were obtained with the erucic acid-derived monomer, reaching a crystalline polymer (Tm — 24.9°C) with molecular weight over 13 kDa. 

Triglycerides and technical-grade fatty acid esters can be used as the starting material in hydroformylation (Scheme 7). Soybean oil and technical-grade methyl oleate were hydroformylated by [RhH(CO)2PPh3)] with triphenylphosphine as the ligand. 

Mecking showed an efficient way to produce a,G>diesters from fatty acid esters yielding excellent monomers for semicrystalline polyesters [63], Some part of the diesters was hydrogenated to diols and was transesterified with the diesters from the hydroesterification of methyl oleate into long-chain polyesters (Scheme 24). The properties of this thermomorphic polymer are related to those of polyethylene. 

The use of isolated fatty acids as substrates for epoxidations has already been reported in 1990 with the epoxidation of methyl oleate and methyl linoleate by MT0/H202 in ferf-butanol. After respectively 24 and 2 h, good yields of either the corresponding diol (methyl oleate) or the monoepoxide (methyl linoleate) are obtained (respectively 92% and 80%) [48]. Under biphasic conditions, the MTO-catalyzed epoxidation of methyl linoleate yields a mixture of mono- and diepoxide (approximately 1 1) at complete conversion after 6 h [79]. Finally, a conjugated methyl linoleate is treated with the MT0/H202 system in biphasic conditions, but here, poor results are obtained after 24 h at room temperature, yielding 26% of the 11,12-monoepoxide and 20% of the 9,10-epoxide [80]. 

The esters of fatty acids and hydrocarbons (Table I, 11-17 with corresponding micrographs and laser diffraction patterns) have all assisted moderately to develop crazes in a stressed polystyrene. The effect of methyl linoleate helped to initiate more crazes than that of methyl oleate (see Figures 11 and 12). As shown in Figures 13 and 14 toluene and xylene assisted in developing more dense but finer crazes as compared with the first two. Note that these chemicals tend to cover the surface of the polystyrene and cause the central region of the diffraction... 

Self-metathesis describes the reachon of an unsaturated fatty acid with itself. For example, methyl oleate gives a mixture of starting material (50%), unsaturated hydrocarbon (25%), and long-chain unsaturated diester (25%), aU as a mixture of T-and trani-isomers. (Figure 18). The diester can be converted to the musk component civetone, but a more efficient route is through self metathesis of the ketone oleon derived from methyl oleate by Claisen condensation (104) (Figure 18). 

Again, it is important to note that methyl esters of lard and tallow are the sum of the methyl esters of fatty acids found in the original fat. Methyl lard for example, will contain methyl myristate, methyl palmitate, methyl stearate, methyl oleate, methyl linoleate, and methyl linolenate in the same percentages as the lard used as the raw material, unless the manufacturer fractionates the material, thereby selecting methyl esters of certain fatty acids over others. 

To elucidate the mechanism of homogeneous hydrogenation catalyzed by Fe(CO)s, kinetic studies were carried out with mixtures of unsaturated fatty esters containing a radioactive label. A C-labeled methyl octadecadienoate-Fe(CO)3 complex was prepared to serve as a catalytic intermediate. Hydrogenation of methyl oleate (m-9-octa-decenoate) and palmitoleate (cis-9-hexadecenoate) and of their mixtures with methyl linoleate was also studied to determine the selectivity of this system, the function of the diene-Fe(CO)3 complex, and the mechanism of homogeneous isomerization. Mixtures of reaction intermediates with a label helped achieve unique simulation of the kinetic data with an analog computer. 

We found previously (10) that in a natural mixture of mono-, di-, and triunsaturated fatty esters the hydrogenation of monoenes with Fe(CO)s was minor. Therefore, competitive hydrogenation studies were carried out with an equal mixture of methyl oleate and linoleate. Diene hydrogenation in such a mixture was indeed dominant (Figure 2). At O.IM initial concentration of Fe(CO)s the formation of stearate was a minor reaction the diene-Fe(CO)3 complex reached a maximum of 4% and remained constant. On the other hand, at 0.5M Fe(CO)5, stearate formation became a more important reaction diene-Fe(CO)3 reached a maximum of 7% and decreased during the course of hydrogenation. Free conjugated dienes were minor products. 

---