Oleic acid, ozonization

Criegee, R., and G. Schjroder. 1960. Direct observation of polymerization in the oleic acid-ozone heterogeneous reaction system by photo electron resonance capture ionization areal mass spectrometry. Chemische Berichte 93 689. 

HOOO(CH2)7COOH. Colourless plates, m.p. lOfi C. Made by the oxidation of oleic acid with ozones. 

Cyanide Wastes. Ozone is employed as a selective oxidant in laboratory-scale synthesis (7) and in commercial-scale production of specialty organic chemicals and intermediates such as fragrances, perfumes (qv), flavors, antibiotics (qv), hormones (qv), and vitamins (qv). In Japan, several metric tons per day (t/d) of piperonal [120-57-0] (3,4-methylenedioxybenzaldehyde) is manufactured in 87% yield via ozonolysis and reduction of isosafrole [93-16-3], Piperonal (or heHotropine [120-57-0]) has a pleasant odor and is used in perfumery. Oleic acid [112-80-1/, CH3(CH2 )7CH—CH(CH2 ). C02H, from tall oil (qv) is ozonated on a t/d scale to produce pelargonic, GgH2yG02H, and azelaic, H02G(GH2)yG02H, acids. Oleic acid also is ozonated in Japan... 

There has been only one major use for ozone today in the field of chemical synthesis the ozonation of oleic acid to produce azelaic acid. Oleic acid is obtained from either tallow, a by-product of meat-packing plants, or from tall oil, a byproduct of making paper from wood. Oleic acid is dissolved in about half its weight of pelargonic acid and is ozonized continuously in a reactor with approximately 2 percent ozone in oxygen it is oxidized for several hours. The pelargonic and azelaic acids are recovered by vacuum distillation. The acids are then esterified to yield a plasticizer for vinyl compounds or for the production of lubricants. Azelaic acid is also a starting material in the production of a nylon type of polymer. 

OZONOLYSIS. (1) Oxidation of an organic material, i.e., tall oil, oleic acid, safflower oil, cyclic olefins, carbon treatment, peracetic acid production by means of ozone. (2) The use ol ozone as a tool in analytical chemistry to locate double bonds in organic compounds and a similar use in synthetic organic chemistry for preparing new compounds. Under proper conditions, ozone attaches itself at the double bond of an unsaturated compound to form an ozonide. Since many ozonides are explosive, it is customary to decompose them in solution and deal with the final product. See also Oxygen. 

Tetrafluoroethane is a hydrofluorocarbon (HFC) or hydro-fluoroalkane (HFA) aerosol propellant (contains hydrogen, fluorine, and carbon) as contrasted to a CFC (chlorine, fluorine, and carbon). The lack of chlorine in the molecule and the presence of hydrogen reduces the ozone depletion activity to practically zero. Hence tetrafluoroethane can be considered as an alternative to CFCs in the formulation of metered-dose inhalers (MDIs). It has replaced CFC-12 as a refrigerant since it has essentially the same vapor pressure. Its very low Kauri-butanol value and solubility parameter indicate that it is not a good solvent for the commonly used surfactants for MDIs. Sorbitan trioleate, sorbitan sesquioleate, oleic acid, and soya lecithin show limited solubility in tetrafluoroethane and the amount of surfactant that actually dissolves may not be sufficient to keep a drug readily dispersed. 

The cleavage of oleic acid to azelaic acid and pelargonic acid with ozone as oxidant is one of the important industrial applications of ozonolysis [2]. However, finding a catalytic alternative to this unsuitable and hard-to-handle oxidant is in the interests of research groups all over the world. The cleavage of internal C=C double bonds by use of a Re, Mo, or W catalyst with H2O2 as oxidant, or a Ru catalyst with peracetic acid [12], is known. 

Derivation By the oxidation of nonyl alcohol or nonyl aldehyde by the oxidation of oleic acid, especially by ozone. 

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. ... 

The trend is toward oxidants that are relatively harmless and that generate no noxious by-products. Oxygen, and materials derived from it, are examples. Ozone is quite toxic itself, but produces no harmful by-products. It is used commercially for the cleavage of oleic acid to azelaic and pelargonic acids.158 Hydrogen peroxide is made from oxygen (4.23).159... 

Inhaled ozone is known to initiate free-radical autooxidation of unsaturated fatty acids in animal pulmonary lipids (Pryor et al., 1981). These reactions lead to the formation of such typical autooxidation products as conjugated dienes and short-chain alkanes like ethane and pentane. Whether these reactions also occur in water treatment is uncertain. Glaze et al. (1988) showed that 9-hexadecenoic acid (83) reacted readily in aqueous solution to form the expected C, and C, aldehydes and acids. Linoleic acid (84) was converted to a mixture of aldehydes and acids (Carlson and Caple, 1977) notably, 3-nonenal (85) was among the products. Isolation of an unsaturated aldehyde is significant because of the high reported toxicity of these compounds. Carlson and Caple (1977) also implied that the epoxide of stearic acid was formed when an aqueous solution of oleic acid was ozonized the product probably derives from an indirect attack on the double bond by peracids or peroxy radicals (Equation 5.39). Nevertheless, it is conceivable that similar reactions could occur in natural waters. 

Azelaic acid (nonanedioic) is produced along with pelargonic acid (nonanoic) by ozonolysis of oleic acid. Oleic acid mixed with nonanoic acid is fed into an ozone absorber against a flow of oxygen gas containing about 2% of ozone. Ozonation occurs at 25-45 °C and external cooling is required. The product is decomposed and oxidized in another vessel at 100 °C (Section 10.4.3). The product is distilled to remove nonanoic and other low-boiling acids and azelaic acid is recovered from the residue by extraction with hot water in which it is soluble. 

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