New method for hydroxylating long‐chain unsaturated fatty acids, esters, alcohols, and hydrocarbons

Abstract

Summary A new method for hydroxylating long‐chain unsaturated compounds is described which involves addition of formic acid at its boiling point to the double bond followed by hydrolysis of the intermediate formate esters. The addition reaction proceeds slowly in the absence of catalysts, but strongly acidic substances, such as perchloric acid, sulfuric acid, and boron fluoride‐acetic acid complex, speed up the addition tremendously. Monohydroxystearic acids can be prepared in good yield by addition of 90–100% formic acid to the double bond of oleic or elaidic acids, methyl oleate, or the unreacted olefinic material separated from the hydrolyzed reaction product of oleic acid with formic acid, followed by hydrolysis. Similarly prepared are dihydroxyoctadecanes from oleyl alcohol, monohydroxyoctadecenoic and dihydroxystearic acids from linoleic acid, monohydroxyhendecanoic acids (isolated as methyl esters) from 10‐hendecenoic (undecylenic) acid, and secondary hexanols from 1‐hexene. Triglycerides are readily formylated if a small amount of mutual cosolvent is employed. Acetic acid in the presence of acidic catalysts also adds to the double bond at its normal boiling point, but yields are lower than with formic acid.

Associating lattice cluster theory and application to modeling oleic acid + formic acid + formoxystearic acid

“…Strong acids are used to obtain technically useful reaction rates, autocatalysis by FA alone is not sufficient . Reaction is only an intermediate step on the way to monohydroxy stearic acid, which can be used, for example, as lubricant …”

Polymerizable monomers from castor oil. I. Vinyl monomers based on undecenoic acid

“…Methyl 10(ll)-hydroxyundecanoate was prepared from undecenoic acid by formylation with 98-100% formic acid in the presence of catalytic amounts of 70% perchloric acid, followed by esterification of the formoxy compound with methanol in the presence of ~-naphthalenesulphonic acid (12).…”

The chemistry of plant cuticles: a study of cutin from Agave americana L

“…When the mixture was subjected to reversed-phase partition chromatography, with paraffin-castor oil (50%, w/w) as stationary phase, only slight resolution was achieved. As it was not possible to obtain pure acid in this way, the mixture was dissolved in formic acid (98-100%) and hydroxylated with performic acid at 500 (Knight, Koos & Swern, 1954;Bergstrom & Piabo, 1954). The reaction product was saponified, worked up in ether and chromatographed on a paraffin-castor oil column.…”