Ozonolysis oleic acid

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... 

Rhodium catalyst is used to convert linear alpha-olefins to heptanoic and pelargonic acids (see Carboxylic acids, manufacture). These acids can also be made from the ozonolysis of oleic acid, as done by the Henkel Corp. Emery Group, or by steam cracking methyl ricinoleate, a by-product of the manufacture of nylon-11, an Atochem process in France (4). Neoacids are derived from isobutylene and nonene (4) (see Carboxylic acids, trialkylacetic acids). 

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. 

Azelaic acid is made by the ozonolysis of another natural product, oleic acid ... 

Muscalure 20, the pheromone of the housefly has been prepared from oleic acid or erucic acid, similarly (Z)-l 1-heneicosene 21, the synergist of muscalure was obtained [189]. The intermediate 22 for the pheromone of the Cabbage looper was prepared using (Z)-methyl-4-octenedioate [166bJ, that was obtained by partial ozonolysis of (Z,Z)-l,5-cyclooctadiene. Similarly disparlure 23, the sex attractant of the gypsy moth, has been synthesized by two successive crossed-couplings with (Z)-4-octene dioate [191],... 

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. 

Fig. 15.48. Decomposition of the asymmetric primary ozonide formed in the ozonolysis of oleic acid. Two different aldehydes and two different carbonyl oxides are formed. In CH2Cl2 these molecules react with each other to form three secondary ozonides. In methanol, on the other hand, the carbonyl oxides react with the solvent to form hydroperoxides.

On an industrial scale, the traditional method for cleavage of carbon-carbon double bonds is ozonolysis, used for the manufacture of azelaic acid and nonanoic acids from oleic acid, and of butane tetracarboxylic acid from tetrahydrophthalic anhydride. The process is effectively a quantitative and mild process.178 However, it is capital and energy intensive. The intermediate ozonide is worked up either reductively or oxidatively to produce the aldehyde, ketone or carboxylic acid. Hydrogen peroxide is the common oxidizing agent used in the second step.179-181 Oxygen can also be used either alone182 or in combination with zeolites.183 Reviews on ozonolysis are available and the reader is directed to reference 184 for further information. 

From studies on the ozonolysis of oleic acid, the author found a new synthesis of w-aminononanoic acid, from which a polyamide, polynonanoamide, is prepared. This polyamide (Nylon 9) has characteristic properties which are as good as Nylon 6—6 and Nylon 6 as a material for synthetic fibers. 

Since 1951, the ozonolysis of oleic acid (I) from sperm oil has been studied in this laboratory good yields of nonyl aldehyde (II), nonanoic acid (III), and azelaic acid (V) have been obtained. 

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. 

Main renewable feedstock for the production of AA is oleic acid (OA), which is cleaved to A A and pelargonic acid (PA) by ozonolysis [7]. Although various catalysts and oxidants [5, 9] for the cleavage of C18 fatty acids and their derivatives to AA have been described in the scientific literature, these have not been used... 

New interesting developments regarding technical processes for the preparation of AA such as biocatalytic oxidation of PA and the two-stage cleavage of oleic acid using H2O2 and O2 as oxidants are reported later in the text. However, ozonolysis coupled with an aerobic oxidative work-up of intermediates is the most important industrial process at the present time [5, 7]. 

Ozonolysis of unsaturated fatty acids and esters, for example, of oleic acid in the production of pelargonic acid... 

Rebrovic, L., The Peroxidic Species Generated by Ozonolysis of Oleic Acid or Methyl Oleate in a Carboxyhc Acid Medium,/. Am. Oil Chem. Soc. 69 159-165 (1992). 

If our labeled linoleic acid is transformed only into acids of the linoleic acid type, the only radioactive aldehyde obtain by reductive ozonolysis of the liver polyenoic acid mixture will be hexanal. Transformation into the oleic acid type would be indicated by radioactive nonanal, and transformation into the hnolenic acid type by radioactive malonic acid after oxidative ozonolysis. 

The same result (7b) was obtained in a comparable experiment with linolenic acid labeled in position 17 (Table II). Here the question was raised of whether a transition to polyenoic acids of the linoleic or oleic acid type occurs by hydrogenation of the double bonds next to the methyl end. In this case reductive ozonolysis would yield not only radioactive propanal but also hexanal and nonanal. It is evident from Table II that the specific activity of hexanal and nonanal is practically zero that of propanal, however, is 9000-12,000 dpm/mg. 

The reaction of excess amounts of methyl acrylate and the self-metathesis products of monounsaturated fatty acids like methyl ester of oleic acid with ethylene, produces valuable monomers for polycondensation polymers, as well as precursors for detergents in the presence of a suitable metathesis catalyst. In oleochemistry, azaleic and pelargonic acid were obtained industrially by ozonolysis of oleic acid. Non-linear fatty acid derivatives with two double bonds, (ricinoleic acid maleate) and one double bond (ricinoleic acid succinate) were produced from ricinoleic acid by esterification with maleic and succinic anhydride, respectively. Hydrogenation of this ricinoleic acid succinate yielded 12-hydroxystearic acid succinate which is a monomer for vegetable oil-based polyester. 

Azelaic acid can be prepared by the oxidation of oleic acid. Sebacic acid can be produced from castor oil. Brassylic acid can be synthesized from erucic acid via an ozonolysis reaction and with the aid of microorganisms from tridecane (55,56). The preparation of brassylic acid from tridecane occurs as follows (56) ... 

Petroselinic acid (18 1 6c) is an isomer of oleic acid which occurs widely in seed oils of the order Umbel-liferae (35-85%) usually along with oleic acid and other saturated and unsaturated acids. The co-occurrence of petroselinic and oleic acids complicates the analysis of these seed oils and the two isomers are usually distinguished after ozonolysis. Kleiman and Spencer (1982) analysed over 200 petroselinic acid-containing oils and designated 14 which were especially rich sources of this acid. The seeds contained 32-50% of oil and the oil had 52-87% of petroselinic acid. 

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