Search for new industrial oils. XI. Oils of boraginaceae

Analysis of seed oils from 29 species of the family Boraginaceae revealed widespread occur-rence of 6,9,12-octadecatrienoic and C₁₈ noncon-jugated tetraenoic acids in addition to linolenic and other common C₁₆ and C₁₈ acids. The 6,9,12-octadecatrienoic acid ranged in amount from 0-27%, tetraene from 0-17%, and linolenic acid from 0.3-50%. Iodine values of the oils ranged from 88-225. A laboratory of the No. Utiliz. Res. and Dev. Div., ARS, USDA. A division of ARS, USDA.     

Search for new industrial oils. V. Oils of cruciferae

Seeds from 37 species of plants in the family Cruciferae were analyzed for oil and protein, and the fatty acid composition of the oils was determined by gas-liquid chromatography. Erucic acid, generally considered characteristic of crucifer oils, occurs in about three-fourths of these species in amounts ranging from 3 to 59%. Some oils free of erucic acid contain up to 63% linolenic acid or up to 58% eicosenoic. Presented at the spring meeting of the American Oil Chemists' Society, St. Louis, Missouri, May 1–3, 1961. A laboratory of the Northern Utilization Research and Development Division. Agricultural Research Service, U. S. Department of Agriculture.     

Search for new industrial oils. XIII. Oils from 102 species of cruciferae

Seed from additional species of Cruciferae have been analyzed for crude protein, oil and fatty acids in the oil. Oils were like those reported earlier from other crucifers, except forCardamine impatiens which is unique among known seed oils because it contains some 25% dihydroxy acids. Erucic acid is present (0.3–55%) in about three-fourths of the 102 samples. Eicosenoic acid is a major constituent (32–53%) in four species and monohydroxy acids (45–72%) in another four. Linolenic acid occurs (2–66%) in oil of all species. Presented at the AOCS meeting in Chicago, Ill., October 11–14, 1964. A laboratory of the No. Utiliz. Res. and Dev. Div., ARS, USDA. ARS, USDA.     

Search for new industrial oils. VII

Seed oils from 37 plant species in 18 families have been analyzed for fatty acid composition by the isomerization method. The variability encountered is evidenced by the range in content of component acids: from 0–23% for apparent linolenic acid, from 8–74% for apparent linoleic acid, and from 2–88% for apparent oleic acid. Dimorphecolic acid has been found to the extent of approximately 60% in a second species ofDimorphotheca, D. pluvialis (L.) Moench, and in the closely related species,Osteospermum ecklonis (DC.) T. Norl.O. spinescens Thunb. contained instead 30% of a conjugated triene, presumably the same as the 8,10,12-octadecatrienoic reported from the relatedCalendula officinalis L. Oils rich in monoenoic acids are mostly in the Umbelliferae and Araliaceae and presumably contain petroselinic acid as well as oleic. Presented at the AOCS meeting in St. Louis, Mo., May 1–3, 1961. A laboratory of the Northern Utilization Research and Development Division, Agricultural Research Service, U.S.D.A. Agricultural Research Service, U.S.D.A.     

Search for new industrial oils. IV

Summary Chemical screening of seed oils continues to reveal nature's diversity. This work provides leads to numerous species which warrant further research to investigate their oil and meal in greater detail, to appraise their crop potential, and to assess their practical value for providing new oilseeds. This is a laboratory of the Northern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture. Agricultural Research Service, U. S. Department of Agriculture.     

Search for new industrial oils. I. Selected oils from 24 plant families

Summary The group of analyses used in this preliminary screening of oils has proved capable of indicating many seed species that contain oils of unusual or unknown composition. Some of the oils are characterized sufficiently to suggest probable commercial uses; others give no evidence of properties that would lead to their use while present commercial oils are in adequate supply. Still other oils are shown to have unknown composition, which must be determined before their potential value can be judged. The study as yet contains too few species to generalize about the relationship between botanical classification and oil composition. It does however provide numerous leads in the search for oils of industrial value. This is a laboratory of the Northern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture. Agricultural Research Service, U. S. Department of Agriculture.     

Search for new industrial oils. XIV. Seed oils of labiatae

Seed of 194 species in 56 genera of Labiatae, representing six of the eight subfamilies, were analyzed for oil and protein and for fatty acid composition of the oil. The oils are diverse and include some that contain up to 70% oleic acid, 79% linoleic acid, or 72% linolenic acid. An allenic function occurs in a third of the samples from the subfamily Stachyoideae and in the one sample analyzed from the Prasioideae. A method for determining the allene was devised. Oils fromTeucrium species containtrans unsaturation in unidentified components. Oils from twoLamium species have both allenic andtrans unsaturation. Two species ofThymus appear to produce hydroxy acids. Presented in part at the AOCS Meeting, Houston, April 1965. No. Utiliz. Res. Dev. Div., ARS, USDA. Crops Research Div., ARS, USDA.     

Search for new seed oils. XV. Oils of boraginaceae

In a search for a preferred source of γ-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 C₂₀ acids and 23% of components more volatile in gas chromatography than the usual triglycerides. Presented at AOCS meeting, New Orleans, May 1967. Earlier papers of this series carried the running title “Search for New Industrial Oils.” The revised title is more appropriate for the basic chemical compositional data reported, that can be useful in a broader context than originally implied. No. Utiliz. Res. Dev. Div., ARS, USDA. ARS, USDA.     

Search for new industrial oils. viii. the genuslimnanthes

Seed oils from most of the known species and varieties ofLimnanthes were analyzed for their fatty acid content. Each contained at least 95% acids with more than 18 carbon atoms. The major component acid,cis-5-eicosenoic, ranged 52–77% of the acids present. Seeds of all species examined contained thioglucosidic precursors of volatile isothiocyanates, liberated by the action of mustard seed enzymes on the meal. One species also yielded a small amount of an oxazolidinethione-like compound of the type associated with enzyme-treated rapeseed meal.     

Search for new industrial oils. VI. Seed oils of the genusLesquerella

Fatty acid composition of seed oil from 14 species of the genusLesquerella has been determined by gas-liquid chromatography. All but two species contain hydroxyeicosenoie acid in amounts ranging from 45 to 74%. The remaining two species contain about 50% C₁₈ hydroxy acids, but none of the C₂₀ hydroxy acid. Presented at the spring meeting of the American Oil Chemists' Society, St. Louis, Missouri, May 1–3, 1961. A laboratory of the Northern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.     

Search for new industrial oils. X. Seed oils of the calenduleae

Seed oils from 29 species in five genera of the tribe Calenduleae, family Compositae, have been examined to determine the distribution of dimorphecolic acid (9-hydroxyl-trans-10,trans-12-octadecadienoic acid) among the close relatives ofDimorphotheca. Dimorphecolic acid occurs in all five of theDimorphotheca species ofOsteospermum in amounts ranging from 34–75% of the oil. In all other species of the tribe analyzed to date, including 14 species ofOsteospermum, two ofCalendula, and two ofChrysanthemoides, the oil contained conjugated trienoic acids ranging from 14–60%. No. Util. Res. and Dev. Div., ARS, USDA. ARS, USDA     

Search for new industrial oils: XVI. Umbelliflorae—seed oils rich in petroselinic acid

Seed oils of the order Umbelliflorae, including those from the families Umbelliferae, Garryaceae, Araliaceae, Cornaceae, Davidiaceae, Nyssaceae and Alangiaceae, were analyzed for fatty acid composition by gas liquid chromatography (GLC) of their methyl esters. The characteristic fatty acid of the order, petroselinic acid, occurred in the Umbelliferae in amounts up to 85%. In the Araliaceae, the content was as high as 83% and in the Garryaceae as high as 81%. The other major acids were palmitic, oleic and linoleic acids, with small amounts of hexadecenoic, stearic, linolenic, and, in some cases, C₂₀ acids. petroselinic acid was determined by microscale ozonolysis of the C₁₈ monoenoic esters and subsequent GLC of the ozonolysis products. The occurrence of high oil contents (up to 46%) combined with exceptionally high (up to 83%) single component purity is notable and emphasizes the potential of the Umbelliflorae as a raw material source for the chemical industry.     

Search for new industrial oils. XII. Fifty-eight euphorbiaceae oils,including one rich in vernolic acid

Seed oil ofEuphorbia lagascae Spreng. contains 57% ofcis-12,13-epoxy-cis-9-octadecenoic (vernolic) acid. The amt of trivernolin in the glycerides of this species indicates random or restricted random distribution of the vernolic acid. Seed from 57 additional species in the Euphorbiaceae were analyzed for oil and protein contents and also for fatty acid composition of the oils. Iodine values (I.V.) of the oils ranged from 87–221. Among these oils, samples were encountered with as much as 76% linolenic, 77% linoleic or 84% oleic acid. Presented at the AOCS in New Orleans, 1964. A laboratory of the No. Utiliz. Res. & Dev. Div., ARS, USDA. ARS, USDA.     

Search for new industrial oils,IX.Cuphea,a versatile source of fatty acids

Seed oils from five species ofCuphea show three distinct patterns of fatty acid composition.C. hookeriana andC. painteri oils contain ca. 70% caprylic acid,C. ignea and C.llavea oils have over 80% capric acid, andC. carthagenensis oil contains 57% lauric and 18% capric acids. No. Utiliz. Res. and Dev. Div., ARS, USDA ARS, USDA     

Whole-plant oils,potential new industrial raw materials

In an extensive screening program, 14 plant species have been identified which have good potential as hydrocarbon- and rubber-producing crops. These plants contain from 5 to 10% oil plus polymeric hydrocarbon on a dry weight basis. Since their dry matter yield should be 11,200 to 22,400 kg/ha/year, they would produce several times as much oil as conventional oilseed crops. In these plants, the oil is not concentrated in storage organs, i.e., seed or fruit tissue, but is distributed throughout the whole plant. Several species are lactiferous, with oil as a major component of the latex. A few which are of primary interest as potential new sources of natural rubber produce an equal yield of by-product oil. A prominent feature of most whole-plant oils is their large component of nonglyceride esters. Such oils could become valuable new feedstocks for production of plasticizers for rubber and plastics and new sources of waxes, long chain alcohols, sterols, terpenes, fatty acids, and other products. A petroleum refinery could be operated on whole-plant oils, and some species are being referred to as potential “gasoline trees.” Presented at the AOCS Meeting, St. Louis, May 1978.     

New nonionic detergents derived from epoxidized oils. III1

A series of 21 nonionic detergents based on epoxidized sperm oil, epoxidized methyl oleate, and epoxidized butyl tallate are discussed. The materials were synthesized by alcholysis of the oxirane oxygen in the presence of boron trifluoride. Benzene was used as a solvent to act as a coupling agent for the unreacted materials. Methoxy polyoxyethylene alcohols were used as the hydrophilic alcohols with which the epoxidized esters were reacted. Physical properties and performance characteristics of the various compounds synthesized are catalogued and the reaction itself is characterized. It is shown that the properties of the materials can be varied by varying both the size of the polyoxyethylene moiety attached to the ester and the characteristics of the ester itself. These materials all appear to be low foaming wetting agents and emulsifying agents. It is felt that these materials offer a definite potential for the use of epxodized natural fats and natural fat derivatives for the custom synthesis of tailor made surface active agents. Being based on naturally occurring straight chain materials they would als be biologically degradable. Presented at the AOCS Meeting, New Orleans, April 1964.     

New crop developments for industrial oils

Traditional industrial fats and oils are derived from inedible tallow or lard, fish and whale oil, and a small group of plant oils, including linseed, soybean, castor, tung, tall, and rapeseed oil. A group of new crops and prospective new crops is available to be utilized advantageously for the production of renewable industrial resources. Some of these plants have been studied extensively from germplasm variation through crop production and processing to evaluation of the final oil and meal products. Others are not developed that far yet. Case histories onCramble, Limnanthes, Lunaria (long chain acids),Lesquerella (hydroxy acids),Stokesia andVernonia (epoxy acids),Calendula (conjugated unsaturation),Cuphea (short chain acids), jojoba (liquid wax esters), andFoeniculum (petroselenic acid) indicate that many obstacles must be overcome to arrive at success.     

The hydrogenation of fatty oils with palladium catalyst. III. Hydrogenation of fatty oils for shortening stock

Summary Palladium-on-carbon catalysts are exceedingly active for the hydrogenation of natural unsaturated oils when very mild conditions are used. Selectivity is usually good, andtrans content can be adequately controlled by the proper choice of conditions. In the range of operating variables used in this work,trans formation is lessened with increased agitation and pressure, decreased catalyst activity, decreased concentration of metal in oil and on carrier, and with decreased temperature. Some shortening stocks were obtained which have good physical properties, as expressed by their dilatometric curves.     

The use of solvents for purifying industrial naphthalene from coal tar distilled oils

The organic chemistry industry is based on organic compounds derived from coal, petroleum and gas. Coal tars derived from the carbonisation process are complex mixtures, of which the polycyclic aromatic hydrocarbons (PAH's) are the main component. One of the most important PAH's is naphthalene, which represents between 10 to 12% of the sample. In recent years, new applications for industrial naphthalene have been developed. However, the naphthalene required for high level industry must be extremely pure. New routes in the purification process are being studied to reduce the economic cost and environmental impact resulting from the increase in demand for pure naphthalene. Any alternative method to that of sublimation for purification in the distillation process and/or catalytic hydrogenation must improve the quality of industrial naphthalene, to make it suitable for the new applications. In the present work, an alternative method for purifying industrial naphthalene has been investigated. A new process based on extraction with solvents such as phosphoric acid and acetic acid is reported and discussed. Industrial naphthalene was purified by means of a new technique and the stability and good properties of the product were verified.