GB755731A - Preparation of formylated or acetylated fatty compounds and corresponding hydroxylated compounds, including isomers thereof - Google Patents

Abstract

Formylated or acetylated fatty compounds are prepared by reacting one or more fatty compounds (as hereinafter defined) with formic or acetic acid at a temperature between about 70 DEG C. and the normal boiling point of the reaction mixture in the presence of a strong mineral acid catalyst, sufficient of the formic or acetic acid being present to allow its addition to a double-bond of the fatty compound. In a modification, formic acid is used as reagent and also as catalyst. The acylated fatty compounds may be hydrolysed yielding corresponding hydroxylated fatty compounds. The fatty compounds used as starting materials are natural and synthetic glycerides of unsubstituted unsaturated fat acids, the fatty acids obtained by hydrolysis of such glycerides, esters of such fatty acids and unsaturated fatty alcohols obtained by the hydrogenation of such glycerides; they include soybean, cotton seed, peanut, lard and olive oils, oleic, elaidic, linolenic, undecylenic and petroselinic acids, the methyl, ethyl and glyceryl esters of these acids, and oleyl alcohol. The strong mineral acid catalyst is preferably per chloric acid but others, e.g. sulphuric acid, may be used. The acylating acid may serve as a solvent but a mutual solvent is usually employed when acylating a glyceride. The products are believed to be isomeric mixtures. The acylated compounds may be used as plasticizers, lubricants and hydraulic fluids; the corresponding hydroxylated compounds may be used for the same purposes and as surface-active agents and components of alkyd resins. In examples (1) oleic acid is refluxed with formic acid using perchloric acid as catalyst yielding formoxy stearic acid which is saponified with caustic soda and acidified to hydroxy-stearic acid; the conversion is substantially unchanged if the acid catalyst is omitted; reference is made to the replacement of the formic acid by acetic acid yielding the acetoxy compound and of the oleic acid by elaidic acid; (2) methyl oleate is reacted as in (1) to give methyl formoxystearate; (3) oleyl alcohol is reacted with formic acid as in (1) yielding formoxy octadecyl formate which is saponified to give hydroxy-stearyl alcohol; (4) linolenic acid containing some oleic acid is similarly formoxylated and the product hydrolysed to a mixture of hydroxy acids which are esterified with methanol and fractionated to yield the methyl esters of hydroxy octadecenoic and dihydroxy-stearic acids; (6) soybean oil is refluxed with formic acid in butyl acetate with perchloric acid as catalyst yielding formoxylated soybean oil.