Oleic acid reactions

OA Oleic acid Reaction temperature 90°C reaction time 24 h. 

The ability of lipases to synthesize the amide bond has been shown (26). Mucor miehei lipase (NOVO tipozyme) has been used in the reaction of laurylamine and oleic acid at 60°C. Water was shown to inhibit the synthesis of this Ai-lauryloleamide (27). 

Substituted Amides. Monosubstituted and disubstituted amides can be synthesized with or without solvents from fatty acids and aLkylamines. Fatty acids, their esters, and acid halides can be converted to substituted amides by reaction with primary or secondary aLkylamines, arylamines, polyamines, or hydroxyaLkylamines (30). Di- -butylamine reacts with oleic acid (2 1 mole ratio) at 200—230°C and 1380 kPa (200 psi) to produce di-A/-butyloleamide. Entrained water with excess -butylamine is separated for recycling later (31). 

Sodium Dispersions. Sodium is easily dispersed in inert hydrocarbons (qv), eg, white oil or kerosene, by agitation, or using a homogenizing device. Addition of oleic acid and other long-chain fatty acids, higher alcohols and esters, and some finely divided soHds, eg, carbon or bentonite, accelerate dispersion and produce finer (1—20 -lm) particles. Above 98°C the sodium is present as Hquid spheres. On cooling to lower temperatures, soHd spheres of sodium remain dispersed in the hydrocarbon and present an extended surface for reaction. Dispersions may contain as much as 50 wt % sodium. Sodium in this form is easily handled and reacts rapidly. For some purposes the presence of the inert hydrocarbon is a disadvantage. 

Sulfated Acids, Amides, and Esters. Reaction with sulfuric acid may be carried out on fatty acids, alkanolamides, and short-chain esters of fatty acids. The disodium salt of sulfated oleic acid is a textile additive and an effective lime soap dispersant. A typical sulfated alkanolamide stmcture is CiiH23C0NHCH2CH20S03Na. Others include the sulfates of mono and diethanolamides of fatty acids in the detergent range. The presence of... 

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 ... 

Copper—cadmium and zinc—chromium oxides seem to provide most selectivity (38—42). Copper chromite catalysts are not selective. Reduction of red oil-grade oleic acid has been accompHshed in 60—70% yield and with high selectivity with Cr—Zn—Cd, Cr—Zn—Cd—Al, or Zn—Cd—A1 oxides (43). The reduction may be a homogeneously catalyzed reaction as the result of the formation of copper or cadmium soaps (44). 

Alkali fusion of oleic acid at about 350°C ia the Varrentrapp reaction causes double-bond isomerization to a conjugated system with the carboxylate group followed by oxidative cleavage to form palmitic acid (75). In contrast, alkaU fusion of riciaoleic acid is the commercial route to sebacic acid [111 -20-6] ... 

A U.S. patent describes the reaction of commercial oleic acid with hydrogen peroxide in acetic acid foUowed by air oxidation using a heavy metal compound and an inorganic bromine or chlorine compound to catalyze the oxidation. ExceUent yields of dibasic acids are obtained (up to 99%) containing up to 72% azelaic acid (55). 

G-19 Dicarboxylic Acids. The C-19 dicarboxyhc acids are generally mixtures of isomers formed by the reaction of carbon monoxide on oleic acid. Since the reaction produces a mixture of isomers, no single chemical name can be used to describe them. Names that have been used include 2-nonyldecanedioic acid, 2-octylundecanedioic acid, l,8-(9)-heptadecanedicarboxyhc acid, and 9-(10)-carboxystearic acid. The name 9-(10)-carboxystearic acid can be used correctiy if the product is made with no double bond isomerization (rhodium triphenylphosphine catalyst system). 

C-19 dicarboxyhc acid can be made from oleic acid or derivatives and carbon monoxide by hydroformylation, hydrocarboxylation, or carbonylation. In hydroformylation, ie, the Oxo reaction or Roelen reaction, the catalyst is usually cobalt carbonyl or a rhodium complex (see Oxo process). When using a cobalt catalyst a mixture of isomeric C-19 compounds results due to isomerization of the double bond prior to carbon monoxide addition (80). 

Carbonylation, or the Koch reaction, can be represented by the same equation as for hydrocarboxylation. The catalyst is H2SO4. A mixture of C-19 dicarboxyhc acids results due to extensive isomerization of the double bond. Methyl-branched isomers are formed by rearrangement of the intermediate carbonium ions. Reaction of oleic acid with carbon monoxide at 4.6 MPa (45 atm) using 97% sulfuric acid gives an 83% yield of the C-19 dicarboxyhc acid (82). Further optimization of the reaction has been reported along with physical data of the various C-19 dibasic acids produced. The mixture of C-19 acids was found to contain approximately 25% secondary carboxyl and 75% tertiary carboxyl groups. As expected, the tertiary carboxyl was found to be very difficult to esterify (80,83). 

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. 

The dimer acids [61788-89-4] 9- and 10-carboxystearic acids, and C-21 dicarboxylic acids are products resulting from three different reactions of C-18 unsaturated fatty acids. These reactions are, respectively, self-condensation, reaction with carbon monoxide followed by oxidation of the resulting 9- or 10-formylstearic acid (or, alternatively, by hydrocarboxylation of the unsaturated fatty acid), and Diels-Alder reaction with acryUc acid. The starting materials for these reactions have been almost exclusively tall oil fatty acids or, to a lesser degree, oleic acid, although other unsaturated fatty acid feedstocks can be used (see Carboxylic acids. Fatty acids from tall oil Tall oil). 

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). 

Acidic Hydrolysis. Hydrolysis of esters by use of water and a mineral acid leads to an equiUbrium mixture of ester, alcohol, and free carboxyHc acid. Complete reaction can only be achieved by removal of alcohol or acid from the equiUbrium. Because esters have poor solubiUty in water, the reaction rate in dilute acids is fairly low. Therefore, emulsifiers such as sulfonated oleic acid or sulfonated aromatic compounds (TwitcheU reagent) are added to facihtate the reaction. 

Examples are given of common operations such as absorption of ammonia to make fertihzers and of carbon dioxide to make soda ash. Also of recoveiy of phosphine from offgases of phosphorous plants recoveiy of HE oxidation, halogenation, and hydrogenation of various organics hydration of olefins to alcohols oxo reaction for higher aldehydes and alcohols ozonolysis of oleic acid absorption of carbon monoxide to make sodium formate alkylation of acetic acid with isobutylene to make teti-h ty acetate, absorption of olefins to make various products HCl and HBr plus higher alcohols to make alkyl hahdes and so on. 

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 reaction of olefin sulfation and its possibilities has been extensively studied [3-10] and it was used to produce alcohol sulfates. Dry distillation of spermaceti gives palmitic acid and cetene-1, which can be sulfated with sulfuric acid to give cetyl-2 sulfate [11]. Other surfactants were obtained from olefins produced from natural substances, such as alcohol sulfates by sulfation of olefins from decarboxylation of oleic acid [12], by sulfation of olefins made by dehydrating hydroabietyl alcohol, by direct sulfation of abietyl alcohol [13,14], or by sulfation of natural terpenes [15]. 

Although, the enzymatic reaction of esters with amines or ammonia have been well documented, the corresponding aminolysis with carboxylic acids are rarer, because of the tendency of the reactants to form unreactive salts. For this reason some different strategies have been used to avoid this problem. Normally, this reaction has been used for the preparation of amides of industrial interest, for instance, one of the most important amides used in the polymer industry like oleamide has been produced by enzymatic amidation of oleic acid with ammonia and CALB in different organic solvents [10]. 

Aldrich 90%) of oleic acid were dissolved in 200 g of 1-octadecene at room temperature. The reaction mixture was heated to 320 °C with a heating rate of 3.3 C/min, and then kept at that temperature for 30 min. When the reaction temperature reached 320 °C, a severe reaction occurred and the initial transparent solution became turbid and brownish black. The resulting solution... 

This study could be extended to the synthesis of iron nanoparticles. Using Fe[N(SiMe3)2]2 as precursor and a mixture of HDA and oleic acid, spherical nanoparticles are initially formed as in the case of cobalt. However, a thermal treatment at 150 °C in the presence of H2 leads to coalescence of the particles into cubic particles of 7 nm side length. Furthermore, these particles self-organize into cubic super-structures (cubes of cubes Fig. ) [79]. The nanoparticles are very air-sensitive but consist of zerovalent iron as evidenced by Mossbauer spectroscopy. The fact that the spherical particles present at the early stage of the reaction coalesce into rods in the case of cobalt and cubes in the case of iron is attributed to the crystal structure of the metal particles hep for cobalt, bcc for iron. 

Cowan Teeter (1944) reported a new class of resinous substances based on the zinc salts of dimerized unsaturated fatty acids such as linoleic and oleic acid. The latter is referred to as dimer acid. Later, Pellico (1974) described a dental composition based on the reaction between zinc oxide and either dimer or trimer acid. In an attempt to formulate calcium hydroxide cements which would be hydrolytically stable, Wilson et al. (1981) examined cement formation between calciimi hydroxide and dimer acid. They found it necessary to incorporate an accelerator, alimiiniiun acetate hydrate, Al2(OH)2(CHgCOO)4.3H2O, into the cement powder. 

The first example of a heterogeneously catalyzed hydroamination of an alkene appeared in a 1929 patent in which it is claimed that NHj reacts with ethylene (450°C, 20 bar) over a reduced ammonium molybdate to give EtNH2 [24]. An intriguing reaction was also reported by Bersworth, who reacted oleic acid with NH3 in the presence of catalysts like palladium or platinum black or copper chromite to give the hydroamination product in quantitative yields [25]. However, this result could not be reproduced [26]. 

The experiments were performed in a CINC V-02 separator also known as the CS-50 (15). Two Verder VL 500 control peristaltic tube pumps equipped with a double pump head (3,2 x 1,6 x 8R) were used to feed the CCS. In case of the enzymatic reaction, the low mix bottom plate was applied. To operate the reactor at a desired temperature, it was equipped with a jacket which was coimected to a temperature controlled water bath with an accuracy of 0.01°C. The CCS was fed with pure heptane and pure water, both with a flow rate of 6 mL/min. Subsequently, the centrifuge was started (40 Hz, which corresponds to 2400 rpm) and the set-up was allowed to equilibrate for a period of 1 h. At this point, the heptane feed stream was replaced by the organic feed stream (oleic acid (0.6M) and 1-bntanol (0.9M) in heptane). After equilibration for 10 minutes, the reaction in the CCS was started by replacing the water stream with the aqueous feed stream (0.1 M phosphate buffer pH 5.6 containing 1 g/1 of the lipase form Rhizomucor miehei). Samples were taken at regular intervals and analysed by GC. 

Based on a study of the reaction of diethylstannyl dicaprylate with some carboxylic acids (oleic, caprylic, caproic add, etc.) it was suggested that oleic acid tends to displace caprylic acid from the inner sphere of a carboxylate-type complex forming a sufficiently stable complex with tin. The spectrum of the initial diethylstannyl dicaprylate revealed a band at 1600 cm-1 which is intermediate between 1570 and 1720 cm-1. The latter bands are associated with vibrations of bonds... 

Examples of this flipping mechanism are seen in cis-trans isomerizations from less stable to more stable isomers which when the reactions are carried out under deuterium. Already mentioned are the isomerizations of oleic acid. Additionally, methyl-(Z)-but-2-enoate isomerizes to its more stable E-isomer with incorporation of substantial amounts of deuterium during deuteriuma-tion over Pd/C (Fig. 2.16). At the same percentage deuteriumation, the saturated product contains in its P-position 90% of the two deuteriums added to... 

SCDs are a family of microsomal Fe-based metalloenzymes. They act on long-chain saturated acyl CoAs and introduce a ds-double bond at the C-9 or C-10 position. For example, SCDs convert stearic acid into oleic acid, and palmitic acid into palmitoleic acid. Monounsaturated FAs constitute a major component of TGs, cholesteryl esters, and phospholipids. The reaction requires molecular 02 and NADH and generates H20 in the process [3,4]. 

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