Synthetic, degradative, analytical and configurational studies of long chain epoxy and hydroxy acids

Abstract

Part I. Synthetic studies. cis-Hydroxylation of Long-chain Olefins. The Woodward cis-hydroxylation procedure, involving the use of iodine and silver acetate in wet acetic acid, has been adapted and applied to the cis-hydroxylation of long-chain olefins. It is a satisfactory method for oxidising these compounds and has some advantages over other methods of cis-hydroxylation. A further cis-hydroxylation procedure, Involving the use of iodine and silver nitrate in acetonitrile has also been developed. Part II. Degradative Studies. The EPOXY Acid in Cameline Oil. A hydroxy acid, isolated from Camelina sativa seed oil, has been shown to be threo-15:16-dihydroxyoctadec-cis-9cis-12-dienolc acid. Infra-red studies indicate that this acid, is present in the oil as glycerides of cis-l5:16-epoxylinolele acid and Is thus closely related to the only other naturally occurring long-chain epoxy acid viz. cis-12:13-epoxyolelc acid. Part III. Analytical Studies. The Occurrence of 9-hydroxy-octadec-cis-12-enoic Acid in Various Strophanthns Oils. 9-Hydroxyoctadec-12-enoic acid has been identified, qualitatively and quantitatively, in ten Strophanthus oils. In two oils a small amount of optically active erythro-9:10-dihydroxystearic acid accompanies the monohydroxy acid and may occur throughout the genus. The oils have been analysed by throe methods and these are discussed comparatively. The analytical results lead to some generalisations and correlations. Part IV. Configurational Studies. 9-Hydroxyoetadec-cis-12-enoic acid has been isolated and three of the four isomeric 9:12:13-trihydroxystearic acids prepared from it. The rotations of these and other hydroxy acids have been measured. It is tentatively suggested that the 9-hydroxy acid has the D-configuration, thus being in the same series as natural riclnoleic acid. Unsuccessful attempts to synthesise long-chain dihydroxy acids, of known configuration, by extension of the chain of optically active tartaric acid are reported and a more suitable synthetic route is suggested.Part I. Synthetic studies. cis-Hydroxylation of Long-chain Olefins. The Woodward cis-hydroxylation procedure, involving the use of iodine and silver acetate in wet acetic acid, has been adapted and applied to the cis-hydroxylation of long-chain olefins. It is a satisfactory method for oxidising these compounds and has some advantages over other methods of cis-hydroxylation. A further cis-hydroxylation procedure, Involving the use of iodine and silver nitrate in acetonitrile has also been developed. Part II. Degradative Studies. The EPOXY Acid in Cameline Oil. A hydroxy acid, isolated from Camelina sativa seed oil, has been shown to be threo-15:16-dihydroxyoctadec-cis-9cis-12-dienolc acid. Infra-red studies indicate that this acid, is present in the oil as glycerides of cis-l5:16-epoxylinolele acid and Is thus closely related to the only other naturally occurring long-chain epoxy acid viz. cis-12:13-epoxyolelc acid. Part III. Analytical Studies. The Occurrence of 9-hydroxy-octadec-cis-12-enoic Acid in Various Strophanthns Oils. 9-Hydroxyoctadec-12-enoic acid has been identified, qualitatively and quantitatively, in ten Strophanthus oils. In two oils a small amount of optically active erythro-9:10-dihydroxystearic acid accompanies the monohydroxy acid and may occur throughout the genus. The oils have been analysed by throe methods and these are discussed comparatively. The analytical results lead to some generalisations and correlations. Part IV. Configurational Studies. 9-Hydroxyoetadec-cis-12-enoic acid has been isolated and three of the four isomeric 9:12:13-trihydroxystearic acids prepared from it. The rotations of these and other hydroxy acids have been measured. It is tentatively suggested that the 9-hydroxy acid has the D-configuration, thus being in the same series as natural riclnoleic acid. Unsuccessful attempts to synthesise long-chain dihydroxy acids, of known configuration, by extension of the chain of optically active tartaric acid are reported and a more suitable synthetic route is suggested.