Fatty linoleic acid

In the area of moleculady designed hot-melt adhesives, the most widely used resins are the polyamides (qv), formed upon reaction of a diamine and a dimer acid. Dimer acids (qv) are obtained from the Diels-Alder reaction of unsaturated fatty acids. Linoleic acid is an example. Judicious selection of diamine and diacid leads to a wide range of adhesive properties. Typical shear characteristics are in the range of thousands of kilopascals and are dependent upon temperature. Although hot-melt adhesives normally become quite brittle below the glass-transition temperature, these materials can often attain physical properties that approach those of a stmctural adhesive. These properties severely degrade as the material becomes Hquid above the melt temperature. 

Separation of Fatty Acids. Tall oil is a by-product of the pulp and paper manufacturiag process and contains a spectmm of fatty acids, such as palmitic, stearic, oleic, and linoleic acids, and rosia acids, such as abietic acid. The conventional refining process to recover these fatty acids iavolves iatensive distillation under vacuum. This process does not yield high purity fatty acids, and moreover, a significant degradation of fatty acids occurs because of the high process temperatures. These fatty and rosia acids can be separated usiag a UOP Sorbex process (93—99) (Tables 8 and 9). 

A USDA report indicates that between 1967 and 1988, butter consumption remained stable at 2 kg per capita, margarine dropped from 5.1 to 4.7 kg, and measured total fat intake per day dropped from 84.6 to 73.3 g (14). This study also projects that the reduced consumption of tropical oils is only temporary and will return to former use levels, possibly even higher. One reason for this projected rise in tropical oil consumption is the knowledge of the beneficial effects of medium-chain length acids high in lauric oils. There is a keen interest in omega-3 fatty acids, as well as linoleic acid, contained in fish oils. 

The antagonisms that exist between unsaturated fatty acids, and carotene and vitamin E are compHcated and largely undefined. Linoleic acid acts as an antivitamin to i7/-a-tocopherol [59-02-9, 1406-18-9, 10191-41-0] (vitamin E) by reducing availabiHty through direct intestinal destmction. Various Hpoxidases destroy carotenes and vitamin A (73). Dicoumarol [66-76-2] (3,3 -methylenebis(4-hydroxycoumarin)) is a tme antimetaboHte of vitamin K [12001 -79-5] but seems to occur only in clover and related materials that are used primarily as animal feeds (74). 

Lipids. Representative fatty acid compositions of the unprocessed triglyceride oils found in the four oilseeds are given in Table 4 (see Fats and FATTY oils). Cottonseed, peanut, and sundower oils are classified as oleic—linoleic acid oils because of the high (>50%) content of these fatty acids. Although the oleic and linoleic acid content of soybean oils is high, it is distinguished from the others by a content of 4—10% of linolenic acid, and hence is called a linolenic acid oil. 

Conjugation as well as geometric and positional isomerization occur when an alkadienoic acid such as linoleic acid is treated with a strong base at an elevated temperature. CycHc fatty acids result from isomerization of linolenic acid ia strong base at about 250°C (58). Conjugated fatty acids undergo the Diels-Alder reaction with many dienophiles including ethylene, propylene, acryUc acid, and maleic anhydride. 

When tallow fatty acids are the feed, stearic acid (actually 60/40 C16/C18) and oleic acids are the products. Solvent separation is also used to separate stearic acid from isostearic acid when hydrogenated monomer is the feed, and oleic acid from linoleic acid when using tall oil fatty acids as feed. 

Liquid—hquid extraction can be used to obtain high purity linoleic acid from safflower fatty acids or linoleic acid from linseed fatty acids using furfural and hexane as solvents (18). High purity linoleic acid has been obtained from sunflower fatty acids using a dimethylformamide and hexane solvent system (19). 

C-21 dicarboxyhc acids are produced by Westvaco Corporation in Charleston, South Carolina in multimillion kg quantities. The process involves reaction of tall oil fatty acids (TOFA) (containing about 50% oleic acid and 50% hnoleic acid) with acryhc acid [79-10-7] and iodine at 220—250°C for about 2 hours (90). A yield of C-21 as high as 42% was reported. The function of the iodine is apparendy to conjugate the double bond in linoleic acid, after which the acryhc acid adds via a Diels-Alder type reaction to form the cycHc reaction product. Other catalysts have been described and include clay (91), palladium, and sulfur dioxide (92). After the reaction is complete, the unreacted oleic acid is removed by distillation, and the cmde C-21 diacid can be further purified by thin film distillation or molecular distillation. 

Structure and Mechanism of Formation. Thermal dimerization of unsaturated fatty acids has been explaiaed both by a Diels-Alder mechanism and by a free-radical route involving hydrogen transfer. The Diels-Alder reaction appears to apply to starting materials high ia linoleic acid content satisfactorily, but oleic acid oligomerization seems better rationalized by a free-radical reaction (8—10). 

The clay-cataly2ed iatermolecular condensation of oleic and/or linoleic acid mixtures on a commercial scale produces approximately a 60 40 mixture of dimer acids and higher polycarboxyUc acids) and monomer acids (C g isomerized fatty acids). The polycarboxyUc acid and monomer fractions are usually separated by wiped-film evaporation. The monomer fraction, after hydrogenation, can be fed to a solvent separative process that produces commercial isostearic acid, a complex mixture of saturated fatty acids that is Hquid at 10°C. Dimer acids can be further separated, also by wiped-film evaporation, iato distilled dimer acids and trimer acids. A review of dimerization gives a comprehensive discussion of the subject (10). 

The yolk is separated from the white by the vitelline membrane, and is made up of layers that can be seen upon careful examination. Egg yolk is a complex mixture of water, Hpids, and proteias. Lipid components iaclude glycerides, 66.2% phosphoUpids, 29.6% and cholesterol [57-88-5] 4.2%. The phosphohpids consist of 73% lecithin [8002 3-5] 15% cephahn [3681-36-7], and 12% other phosphohpids. Of the fatty acids, 33% are saturated and 67% unsaturated, including 42% oleic acid [112-80-1] and 7% linoleic acid [60-33-3]. Fatty acids can be changed by modifying fatty acids ia the laying feed (see... 

Lipoxygenase-Catalyzed Oxidations. Lipoxygenase-1 catalyzes the incorporation of dioxygen into polyunsaturated fatty acids possessing a l(Z),4(Z)-pentadienyi moiety to yield ( ),(Z)-conjugated hydroperoxides. A highly active preparation of the enzyme from soybean is commercially available in purified form. From a practical standpoint it is important to mention that the substrate does not need to be in solution to undergo the oxidation. Indeed, the treatment of 28 g/L of linoleic acid [60-33-3] with 2 mg of the enzyme results in (135)-hydroperoxide of linoleic acid in 80% yield... 

The word essential as applied to naturally occuning organic substances can have two different meanings. For exanple, as used in the previous section with respect to fatty acids, essential means necessary. Linoleic acid is an essential fatty acid it must be included in the diet for animals to grow properly because they lack the ability to biosynthesize it directly. 

Some fatty acids are not synthesized by mammals and yet are necessary for normal growth and life. These essential fatty aeids include llnoleic and y-linolenic acids. These must be obtained by mammals in their diet (specifically from plant sources). Arachidonic acid, which is not found in plants, can only be synthesized by mammals from linoleic acid. At least one function of the essential fatty acids is to serve as a precursor for the synthesis of eicosanoids, such as... 

Polyunsaturated fatty acids pose a slightly more complicated situation for the cell. Consider, for example, the case of linoleic acid shown in Figure 24.24. As with oleic acid, /3-oxidation proceeds through three cycles, and enoyl-CoA isomerase converts the cA-A double bond to a trans-b double bond to permit one more round of /3-oxidation. What results this time, however, is a cA-A enoyl-CoA, which is converted normally by acyl-CoA dehydrogenase to a trans-b, cis-b species. This, however, is a poor substrate for the enoyl-CoA hydratase. This problem is solved by 2,4-dienoyl-CoA reductase, the product of which depends on the organism. The mammalian form of this enzyme produces a trans-b enoyl product, as shown in Figure 24.24, which can be converted by an enoyl-CoA isomerase to the trans-b enoyl-CoA, which can then proceed normally through the /3-oxidation pathway. Escherichia coli possesses a... 

Organisms differ with respect to formation, processing, and utilization of polyunsaturated fatty acids. E. coli, for example, does not have any polyunsaturated fatty acids. Eukaryotes do synthesize a variety of polyunsaturated fatty acids, certain organisms more than others. For example, plants manufacture double bonds between the A and the methyl end of the chain, but mammals cannot. Plants readily desaturate oleic acid at the 12-position (to give linoleic acid) or at both the 12- and 15-positions (producing linolenic acid). Mammals require polyunsaturated fatty acids, but must acquire them in their diet. As such, they are referred to as essential fatty acids. On the other hand, mammals can introduce double bonds between the double bond at the 8- or 9-posi-tion and the carboxyl group. Enzyme complexes in the endoplasmic reticulum desaturate the 5-position, provided a double bond exists at the 8-position, and form a double bond at the 6-position if one already exists at the 9-position. Thus, oleate can be unsaturated at the 6,7-position to give an 18 2 d5-A ,A fatty acid. 

Mammals can add additional double bonds to unsaturated fatty acids in their diets. Their ability to make arachidonic acid from linoleic acid is one example (Figure 25.15). This fatty acid is the precursor for prostaglandins and other biologically active derivatives such as leukotrienes. Synthesis involves formation of a linoleoyl ester of CoA from dietary linoleic acid, followed by introduction of a double bond at the 6-position. The triply unsaturated product is then elongated (by malonyl-CoA with a decarboxylation step) to yield a 20-carbon fatty acid with double bonds at the 8-, 11-, and 14-positions. A second desaturation reaction at the 5-position followed by an acyl-CoA synthetase reaction (Chapter 24) liberates the product, a 20-carbon fatty acid with double bonds at the 5-, 8-, IT, and ITpositions. 

FIGURE 25.15 Arachidonic acid is synthesized from linoleic acid in enkaryotes. This is the only means by which animals can synthesize fatty acids with double bonds at positions beyond C-9. 

More than LOO different fatty acids are known, and about 40 occur widely. Palmitic acid (C ) and stearic acid (Cjy) are the most abundant saturated fatty adds oleic and linoleic acids (both Care the most abundant unsaturated ones. Oleic acid is monounsaturated since it has only one double bond, whereas linoleic, linolenic, and arachidonic acids are polyunsaturated fatty acids because they have more than one double bond. Linoleic and linolenic... 

By depolymerizing PET waste with a polyol and subsequently condensing the oligomeric product with a polycarboxylic acid or anhydride, polyester resins are produced which have wide industrial applications. Depending on the polyol and polycarboxylic acid or anhydride used, saturated resins, alkyd resins, or unsaturated resins are obtained. PET wastes have been used for the production of alkyd resins in water thinnable paints. The materials obtained from the reaction of PET with a mixture of fatty acids high in linoleic acid content and trimethylolethane have been used in the preparation of water-dispersible coatings. Products of the depolymerization of PET with trimethylolpropane and pentaerythritol are used in the manufacture of high-solids paints. In the first step, PET is depolymerized with trimethylopropane and pentaerythritol at temperatures of 230-240°C. The final paint compositions contain 30-50% of PET depolymerization products.12... 

A soap-based powder can be produced in combination with ester sulfonates. Thirty-five percent of a sodium soap mixture (5% lauric acid, 5% myristic acid, 52% palmitic acid, 21% stearic acid, 12% oleic acid, and 5% linoleic acid) is mixed with 15% sodium a-sulfo palm oil fatty acid methyl ester, 3% lauric acid ethoxylate, 5% sodium silicate, 17% sodium carbonate, 20% Na2S04- 10H2O, and 5% water [79]. 

Oleic acid, linolic acid, ricinolic acid, and 2-bromostearic acid methyl ester as well are reacting with diethyl phosphite in the presence of benzoyl peroxide to the corresponding phosphono fatty acid esters [156-158]. 

Figure 22-4. Sequence of reactions in the oxidation of unsaturated fatty acids, eg, linoleic acid. A -c/s-fatty acids or fatty acids forming A -c/s-enoyl-CoA enter the pathway at the position shown. NADPH for the dienoyl-CoA reductase step is supplied by intramitochondrial sources such as glutamate dehydrogenase, isocitrate dehydrogenase,and NAD(P)H transhydrogenase.

Linoleic and a-linolenic acids are the only fatty acids known to be essential for the complete nutrition of many species of animals, including humans, and are known as the nutritionally essential fatty acids. In most mammals, arachidonic acid can be formed from linoleic acid (Figure 23-4). Double bonds can be intro-... 

Separation of fatty acids (Ruthven, 1997). Tall oil from the pulp and paper industry is subjected to separation of rosin acid, linoleic acid, oleic acid, and neutral compounds. Distillation at reduced pressure is u.sed, but this leads to degradation of products. A Sorbex process eliminates this problem. 

Tall oil fatty acids consist of resin acids (25% to 30%) and of a mixture of linolic acid, conjugated Cig fatty acids (45% to 65%), oleic acid (25% to 45%), 5,9,12-octadecatrienic acid (5% to 12%), and saturated fatty acids (1% to 3%). Resin acids are abietinic acid, dehydroabietic acid, and others. Properties of fatty acids are shown in Table 6-1. 

---