9,11-Linoleic acid

Comparatively pure linoleic acid can be obtained, for example, by the purification of safflower oil fatty acid such as low temperature recrystallization method, distillation method, urea method, salt recrystallization method, etc. Source Seki 1971 

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The linoleic acid series, C H2 -402, with two double bonds. 

Linoleic acid [463-40-1] Linoleic acid [60-33-2] Linoleic acid [60-33-3]... 

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. 

Multiply unsaturated linolenic and linoleic acid residues make triglycerides more vulnerable to oxidative degradation than oleic acid which is relatively stable. It is therefore desirable to hydrogenate the most unsaturated residues selectively without production of large quantities of stearic (fully saturated) acid. The stepwise reduction of an unsaturated oil may be visualized as ... 

If first-order kinetics are assumed, k /is the linoleic selectivity ratio and k l is the selectivity ratio for reduction of linoleic acid to stearic acid. Figure 2 shows a typical course of hydrogenation for soybean oil the rate constants are = 0.367, = 0.159, and k = 0.013. With a selective nickel catalyst,... 

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). 

Refluxing linoleic acid and a primary or secondary alkyl amine with -toluenesulfonic acid in toluene for 8—18 h also yields the substituted amides (32—34). The reaction of methyl esters with primary or secondary amines to make substituted amides is catalyzed with sodium methoxide. Reactions are rapid at 30°C under anhydrous conditions (35). Acid chlorides can also be used. Ai,A/-dibutyloleamide [5831-80-17 has been prepared from oleoyl chloride and dibutyl amine (36). 

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. 

Liquid Ghromatography/Mass Spectrometry. Increased use of Hquid chromatography/mass spectrometry (Ic/ms) for stmctural identification and trace analysis has become apparent. Thermospray Ic/ms has been used to identify by-products in phenyl isocyanate precolumn derivatization reactions (74). Five compounds resulting from the reaction of phenyUsocyanate and the reaction medium were identified two from a reaction between phenyl isocyanate and methanol, two from the reaction between phenyl isocyanate and water, and one from the polymerisation of phenyl isocyanate. There were also two reports of derivatisation to enhance either the response or stmctural information from thermospray Ic/ms for linoleic acid hpoxygenase metabohtes (75) and for cortisol (76). 

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). 

Pressure, kPa Caproic acid Caprylic acid Cap tic acid Laurie acid Myristic acid Palmitic acid Stearic acid Oleic acid Linoleic acid... 

Expressed as linoleic acid. Minimum value given. 

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). 

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