Oleoyl chloride

Seventy grams (0.25 mole) of oleic acid (Note 1) is placed in the dropping funnel H of the tangential apparatus (Fig. 2 Note 2). The thionyl chloride distillation is started and regulated (Note 2) the upper part of the column should be filled with the vapor, and reflux should be constant and steady. The add is dropped in at the top of the column over a period of 35 minutes (120 g. per hour). The product that collects in the receiver I contains about 25-27% of thionyl chloride (Note 2) if the heated lower leg K is employed. The product in 

The crude acid chloride will serve for most purposes. It can be distilled at very low pressures (b.p. 99-109°/25 /x) to yield a water-white product d 1.4580-1.4613 (Note 5). Small amounts of oleoyl chloride may be distilled at higher pressures b.p. 180-185°/l-2 mm. The infrared absorption curve of the oleic acid obtainable by hydrolysis is the same as that of the oleic acid used thus no isomerization during the reaction is indicated. 

The oleic acid used by the submitters had a freezing point of — 2° to +13° and a boiling point of 182-187°/l-2 mm. It was a 90% middle cut from Emerson 233 as obtained from Emery Industries, Inc., Cincinnati, Ohio. The checkers found that the amount of color in the product was a function of the purity of the oleic acid. The product from distilled Emerson 233 was dark red-brown, whereas that from a purified grade of oleic acid was pale yellow. 

K the excess escapes at the top through the side arm D which is connected to a Friedrichs condenser E. The bottom of the condenser is connected to a Y-shaped section with an outlet F for effluent gas and a return G which extends below the surface of the liquid in the reservoir. At the top of the column is a 250-ml. dropping funnel H for admitting reactants to the column. Since oleic acid is a liquid at room temperature, heating of this funnel is not required in the present preparation. At the bottom of the column is a 500-ml. flask I for receiving the product. 

The described procedure is not suitable for all acids. For instance, the acid chloride must not have a boiling point so near that of thionyl chloride that they are inseparable by distillation. Certain high-molecular-weight acids give dehydration products, presumably diketenes e.g., behenic and dihydroxystearic acids. 

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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). 

The residue of a sample of olein chloride (crude oleoyl chloride) was tipped into a waste container containing acid tars (70-80% waste sulfuric acid). There was a vigorous reaction, with gas evolution, which sprayed the analytical technician involved with the liquid contents of the container, causing bums. 

Nitro-4-cresol was to be manufactured by adding 4-toluidine to nitric acid. One carboy of nitric acid was charged into the reactor, but the next one charged actually contained oleoyl chloride in error. The violent reaction ensuing ruptured the reactor and there was a fire. 

Oleoyl chloride has been prepared by treatment of oleic acid with thionyl chloride,3 phosphorus trichloride or pentachloride, and oxalyl chloride.4 The highest yield (86%) reported was secured by use of oxalyl chloride in carbon tetrachloride, but the more economical phosphorus trichloride gave a yield of 60%. The standard procedures for obtaining aliphatic acid chlorides have been described many times without inclusion of details other than physical properties. Only references to the procedures useful in the laboratory are given. 

This preparation and oleoyl chloride (p. 66) illustrate the use of the general form of a laboratory-sized continuous reactor.6 This device has many advantages over the commonly used flasks (batch procedure). In particular, the short time of exposure to heat results in a better quality of product, as shown by less color, fewer side reactions, and better melting point, often unchanged by recrystallization. Furthermore, the unlimited capacity, very short reaction time, and use of concentrated solutions permit a larger output with no increase in size of apparatus and less delay required for removal of solvents. 

Isophthaloyl chloride, 2888 f Isopropyl chloroformate, 1560 Methanesullinyl chloride, 0435 Methoxyacetyl chloride, 1165 4-Methoxybenzoyl chloride, 2930 f Methyl chloroformate, 0599 Oleoyl chloride, 3772 Oxalyl dibromide, 0583 Oxalyl dichloride, 0605... 

See Nitric acid Oleoyl chloride See other ACYL HALIDES... 

Isophthaloyl chloride, 2883 f Isopropyl chloroformate, 1555 Methanesulfinyl chloride, 0434 Methoxyacetyl chloride, 1161 4-Methoxybenzoyl chloride, 2925 f Methyl chloroformate, 0732 Oleoyl chloride, 3766 Oxalyl dibromide, 0580 Oxalyl dichloride, 0602... 

Cyanoeslerification. A typical plant type-IV cyanolipid (1) can be prepared by reaction of methacrolein with oleoyl chloride and KCN in the presence of 18-crown-6 in toluene at room temperature (equation 1). 

Ethyl oleate is prepared by the reaction of ethanol with oleoyl chloride in the presence of a suitable hydrogen chloride acceptor. 

Octyl alcohol, 34, 3 -Octyl fluoride, 36, 42 1-Octyl nitrite, 38, 75 Olefins from amine oxides, 39, 41, 42 Oleic acid, 37, 66, 68, 77 39, 15 Oleoyl chloride, 37, 66 Orthocarbonic acid, tetraethyl ESTER, 32, 68... 

Allen and co-workers at the Eastman laboratories developed a procedure for the preparation of oleoyl chloride and other acid chlorides sensitive to heat in a continuous reaction with countercurrent distillation such that the heat-sensitive acid chloride is heated for only a few minutes. Oleoyl chloride of satisfactory purity was obtained in yield of 97-98%. 

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