The reaction of mercaptoacetic acid with methyl linoleate and linoleic acid

Summary The reaction of mercaptoacetic acid with methyl linoleate and with linoleic acid was investigated. The reaction proceeded at low and erratic rates, with and without catalysts, such as peroxides at various temperatures, but could be accelerated by use of a large excess of mercaptoacetic acid. Addition of 1 mole of mercaptoacetic acid to 1 mole of methyl linoleate resulted in a product containing about 40% of mono‐adduct. Ozonolysis of the purified mono‐adduct yielded approximately equimolar quantities of caproic and azelaic acids, indicating that addition occurred about equally at the 9,10‐ and 12,13‐ethylenic bonds. The dicarboxylic acid and the dimethyl ester of the mono‐adduct and the tricarboxylic acid and trimethyl ester of the di‐adduct of linoleic acid and mercaptoacetic acid were prepared, and the infrared spectra and some physical and chemical characteristics of these products were determined. The infrared spectra of the reaction products were obtained and correlated with functional groups which give rise to them. Bands at about 7.8 and 8.8 μ, commonly observed in long chain acids and esters and ascribed to C−O vibrations, are intensified in the sulfur‐containing reaction products, suggesting characteristic absorption of C−S compounds at almost identical wavelengths. The formation of adducts was accompanied by a high degree of isomerization of the unreacted ethylenic bonds from thecis to thetrans form both in the mono‐adduct and in unreacted methyl linoleate. The methyl linoleate recovered contained about 12% diene conjugation, but catalytic quantities of mercaptoacetic acid were not effective in inducing conjugation.