TheTrans-6 fatty acids ofPicramnia sellowii seed oil.

The C18 monoenoic acids inPicramnia sellowii Planch. seed oil include bothcis-andtrans-6-octadecenoic acids, as well as oleic acid. The hexadecenoic acids are also thecis- andtrans-Δ6-isomers, and the eicosenoic acids have Δ6-unsaturation of undetermined geometric configuration. The C18 polyenoic acids detected are 9,12- and 6,9-octadecadienoic and 9,12,15- and 6,9,12-octadecatrienoic acids. Partial investigation of another species,P. pentandra Sw., revealed its oil to have a similar fatty acid composition.

Oxygenated fatty acids of oil from sunflower seeds after prolonged storage.

Chemical analysis of a number of sunflower (Helianthus annuus) seed oil samples revealed a low and variable percentage of hydrogen bromide-reactive material. To characterize the compounds responsible for this reactivity, oil was extracted from selected introductions from Uruguay, Turkey, and Yugoslavia that had been subjected to prolonged storage. Two epoxy fatty acids and two conjugated dienolic acids were isolated from the methyl esters derived from these sunflower seed oils by using a combination of column chromatography and countercurrent distribution. The epoxy acids arecis-9,10-epoxystearic acid (0.5%) andcis-9,10-epoxy-cis-12-octadecenoic (coronaric) acid (2.2%). Characterization of the dienols revealed that they are 9-hydroxy-trans-10,cis-12-octadecadienoic acid (1.2%) and 13-hydroxy-cis-9,trans-11-octadecadienoic acid (1.3%). Fresher seed of some of these introductions contained less of the oxygenated components.Oil from recently produced seed of selected high-oil Russian sunflower varieties, including some currently grown in the United States, contained no more than trace amounts of oxygenated acids. Though the relative contributions of genetic and environmental factors toward genesis of oxygenated acids are not established, increase of those acids in some sunflower lines as a result of storage has been demonstrated.

Structure and intraglyceride distribution of coriolic acid.

Coriolic [(R)-13-hydroxy-cis-9,trans-11-octadecadienoic] acid (III, R=Z=H) was isolated as the methyl ester from twoCoriaria seed oils in 66 and 68% yields. The double bonds and hydroxyl group were located by periodate-permanganate oxidation before, and chromic acid oxidation after, hydrogenation of the double bonds. Alternatively the positions of the functional groups were indicated by a convenient micro-ozonolysis-gas-liquid chromatographic procedure. Determination of products from partial hydrolysis of theCoriaria oils with pancreatic lipase (EC 3.1.1.3) revealed a preference of the corioloyl group for the 1,3-positions in triglyceride molecules. The possible significance of coriolic acid as an intermediate in the biogenetic conversion of linoleic acid to conjugated trienoic acids is discussed.

Glyceride structure ofCardamine impatiens L. Seed oil.

A group of unusual triglycerides, in which one of the acyl groups is a vicinal dihydroxy acid with one of the hydroxyl groups acetylated, has been isolated fromCardamine impatiens L. (Cruciferae) seed oil. Hydrolysis of these triglycerides with castor bean lipase facilitated isolation and identification of a mixture of C(18), C(20), C(22), and C(24) hydroxy acetoxy fatty acids. Pancreatic lipase hydrolysis data revealed that these monoacetylated dihydroxy acid residues are esterified exclusively with one of the alpha-positions of the glycerol moiety. The remaining acyl groups are comprised of ordinary C(18) unsaturated acids (which occupy 98% of the beta-position), palmitic acid, and C(20), C(22), and C(24) monoenoic fatty acids.

Caltha palustris L. Seed Oil. A source of four fatty acids withcis-5-unsaturation.

The seed oil ofCaltha palustris L. yields two unusual polyunsaturated components, all-cis-5,11,14-eicosatrienoic acid (23%) and all-cis-5,11,14,17-eicosatetraenoic acid (1%). The C(18) monoene fraction (26%) is a mixture ofcis-5- andcis-9-octadecenoic acids (2ratio1). The C(20) monoene fraction (12%) is a mixture ofcis-11- andcis-5-isomers (3ratio1).

Search for new seed oils. XV. Oils of boraginaceae.

In a search for a preferred source of gamma-linolenic (all-cis-6,9,12-octadecatrienoic) acid, seed oils of 33 species of Boraginaceae were examined. The desired triene was found primarily in the subfamily Boraginoideae in amounts ranging from 0.2 to 18%. Oils of this subfamily also contain 0.2 to 15% of the tetraene, all-cis-6,9,12,15-octadecatetraenoic acid. Total unsaturation and the relative proportions of the common acids varied widely in oils of the family. Monoene predominated in the subfamily Cordioideae, diene in Heliotropioideae, and a diverse composition among the Boraginoideae; seven had iodine values of 200 or above.Cordia verbenacea seed oil was unique among those examined in having 43% of C(20) acids and 23% of components more volatile in gas chromatography than the usual triglycerides.

An octadecatrienoic acid from Lamium purpureum L. seed oil containing 5,6-allenic and trans-16-olefinic unsaturation.

1. Lamium purpureum L. (Labiatae) seed oil contains 16% of a new acid characterized as (-)-octadeca-5,6-trans-16-trienoic acid (proposed trivial name ;lamenallenic acid') (Ia). The acid was isolated as its methyl ester by countercurrent distribution by using a combination of recycle-single withdrawal techniques. Methyl lamenallenate (Ib) is strongly laevorotatory. 2. The structure was established by infrared spectroscopy, nuclear-magnetic-resonance spectroscopy, quantitative hydrogenation and oxidative cleavage data of the original acid and of hydrazine partial reduction products. 3. Other unsaturated esters identified by their cleavage products were oleate, linoleate and linolenate. 4. A very small amount (less than 1%) of methyl laballenate [(-)-methyl octadeca-5,6-dienoate] was also isolated and identified.

(S)-1,2-diacyl-3-acetins: Optically active triglycerides fromEuonymus verrucosus seed oil.

The seed oil ofEuonymus verrucosus Scop., family Celastraceae, contains more than 90% 1,2-diacyl-3-acetins (monoacetotriglycerides). The constituent triglyceride acids, other than acetic, are the usual long-chain fatty acids.Thin-layer chromatography (TLC), infrared (IR) and hydrolysis with pancreatic lipase indicate that the acetic acid is esterified exclusively on the outer glycerol carbon atoms. The isolated mixed monoacetotriglycerides exhibit optical rotation caused by asymmetry of the central glycerol carbon atom. Comparison with synthetic products of known configuration shows that the natural material is essentially all (S)-1,2-diacyl-3-acetin.IR, TLC and GLC analyses indicate the presence of monoacetotriglycerides in seven other species of Celastraceae and five species in three other plant families in amounts from 13 to 98%.