Abstract
Fatty acids containing oxirane functional groups have unexpectedly been found in wide distribution in seed oils, usually present as longchain glycerides. Four such acids have been discovered:cis- andtrans-9,10-epoxystearic acid; vernolic (cis-12,13-epoxyoleic) acid; coronaric acid, isomeric with vernolic acid but with the oxirane and double-bond functions in the reverse positions; andcis-15,16-epoxylinoleic acid. No single analytical tool has been universally successful in measuring the oxirance content of epoxides. This appears to be caused by the way in which the chemical reactivity of the three-membered cyclic ether is modified by molecular structure and by the presence of nearby substituents.
A survey of the published methods for the determination of oxirane functions, including mention of the nature of interfering substances, is given. Techniques used to overcome some of these difficulties are discussed. These procedures include the use of chromatographic and spectrophotometric procedures to solve some of the analytical problems which are encountered. Special consideration is given to vernolic acid and its glycerides since this is the most widely distributed and abundant epoxy acid found in seed oils to date.
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References
Anders, M. W., and G. J. Mannering J. Chromatog.7, 258–260 (1962).
Barford, R. A., S. F. Herb, F. E. Luddy, P. Magidman and R. W. Riemenschneider, JAOCS40, 136–138 (1963).
a) Bentz, A. P., and J. H. Fioriti, presented in part at the First World Fat Congress, Hamburg, Germany, in October 1964, and at the AOCS Meeting in Houston, Tex., April 1965; b) Fioriti, J. A., A. P. Bentz and R. J. Sims, JAOCS43, 37–41 (1966); c) Fioriti, J. A., A. P. Bentz and R. J. Sims, Ibid. 43, 487–490 (1966).
Bolley, D. S., R. J. Gall, W. F. Goldsmith, G. Maerker, W. D. Pohle, R. J. Sobatzki, R. O. Walker and D. O. Barlow, JAOCS41, 86–87 (1964).
Booth, A. N., personal communications, 1962–1967.
Cahn, R. S., C. K. Ingold and V. Prelog, Experientia12, 81–94 (1956).
Caius, J. F., and K. S. Mhaskar, Indian J. Med. Res.11, 337–346 (1923).
Chalvardjian, A., L. J. Morris and R. T. Holman, J. Nutr.76, 52–58 (1962).
Chapman, D., J. Chem. Soc. 131–138 (1963).
Chem. and Eng. News45, No. 4, 34–35 (1967).
Chisholm, M. J., and C. Y. Hopkins, Chem. Ind. (London) 1154–1155 (1959).
Curl, A. L., and M. S. White, J. Food Sci.27, 171–176 (1962).
Daubert, B. F., and E. S. Lutton, J. Am. Chem. Soc.69, 1449–1451 (1947).
Durbetaki, A. J., Anal. Chem.28, 2000–2001 (1956).
Earle, F. R., A. S. Barclay and I. A. Wolff, Lipids1, 325–327 (1966).
Earle, F. R., E. H. Melvin, L. H. Mason, C. H. van Etten, I. A. Wolff and Q. Jones, JAOCS36, 304–307 (1959); b) Earle, F. R., T. A. McGuire, J. Mallan, M. O. Bagby, I. A. Wolff and Q. Jones, Ibid.37, 48–50 (1960); c) Earle, F. R., I. A. Wolff and Q. Jones, Ibid.37, 254–256 (1960); d) Earle, F. R., C. A. Glass, G. C. Geisinger, I. A. Wolff and Q. Jones, Ibid.37, 440–447 (1960); e) Mikolajczak, K. L., T. K. Miwa, F. R. Earle and I. A. Wolff, Ibid.38, 678–681 (1961); f) Mikolajczak, K. L., F. R. Earle and I. A. Wolff. Ibid.39, 78–80 (1962); g) Earle, F. R., I. A. Wolff, C.A. Glass and Q. Jones, Ibid.39, 381–383 (1962); h) Miller, R. W., M. E. Daxenbichler, F. R. Earle and H. S. Gentry, Ibid.41, 167–169 (1964); i) Miller, R. W., F. R. Earle, I. A. Wolff and Q. Jones, Ibid.41, 279–280 (1964); j) Earle, F. R., K. L. Mikolajczak, I. A. Wolff and A. S. Barclay, Ibid.41, 345–347 (1964); k) Kleiman, R., F. R. R., C. R. Smith Jr., S. G. Yates and Q. Jones, Ibid.42, 169–172 (1965); m) Miller, R. W., F. R. Earle, I. A. Wolff and Q. Jones, Ibid.42, 817–821 (1965).
Enslin, P. R., T. W. Naudé, D. J. J. Potgieter and A. J. van Wyk, Tetrahedron22, 3213–3220 (1966).
Ghosh, J. C., Pharmaceut. J. and Pharmacist121, 54–55 (1928).
Gleason, H. A., Bull. N. Y. Bot Gard.4, 144–243 (1906).
Greenspan, F. P., W. O. Lundberg, W. D. Schroeder, D. Swern, J. G. Wallace and K. E. Holt, JAOCS34, 476–477 (1957).
Gunstone, F. D., J. Chem. Soc. 1611–1616 (1954).
Gunstone, F. D., Chem. Ind. (London) 1551–1554 (1966).
Gunstone, F. D., and L. J. Morris, J. Chem. Soc. 2127–2132 (1959).
Haeberer, E. T., and G. Maerker, JAOCS40, 274–275 (1963).
Harris, J. A., F. C. Magne and E. L. Skau, Ibid.40, 718–720 (1963).
Hassan, M. M., and C. H. Lea, Chem. Ind. (London) 1760 (1965).
Herb, S. F., P. Magidman and R. A. Barford, JAOCS41, 222–224 (1964).
Herb, S. F., P. Magidman and R. W. Riemenschneider, Ibid.37, 127–129 (1960).
Hopkins, C. Y., “Progress in the Chemistry of Fats and Other Lipids,” Vol. VIII, Part 2, Pergamon Press, Oxford, 1965, pp. 213–252.
Hopkins, C. Y., and M. J. Chisholm, “Fatty Acids of Kenaf Seed Oil,” presented at the AOCS Meeting, Cincinnati, September 30–October 2, 1957; b) JAOCS36, 95–96 (1959).
Hopkins, C. Y., and M. J. Chisholm, Ibid.37, 682–684 (1960); b) Hopkins, C. Y., and M. J. Chisholm, Chem. Ind. (London) 1134 (1960); c) Ewing, D. F., and C. Y. Hopkins, Can. J. Chem.45, 1259–1264 (1967).
Jay, R. R., Anal. Chem.36, 667–668 (1964).
King, G., Nature164, 706–707 (1949).
King, G., J. Chem. Soc. 1980–1984 (1951).
Krewson, C. F., and J. S. Ard, U. S. Patent 3,165,540 (1965).
Krewson, C. F., J. S. Ard and R. W. Riemenschneider, JAOCS39, 334–340 (1962).
Krewson, C. F., and F. E. Luddy, Ibid.41, 134–136 (1964).
Krewson, C. F., C. L. Ogg, F. J. Oelshlegel Jr., R. Hale and A. H. Hale, Ibid.42, 563–565 (1965).
Krewson, C. F., G. R. Riser and W. E. Scott, Ibid.43, 377–379 (1966).
Krewson, C. F., and W. E. Scott, Ibid.41, 422–426 (1964).
Krewson, C. F., and W. E. Scott, Ibid.43, 171–174 (1966).
Krewson, C. F., and W. E. Scott, U. S. Patent 3,230,239 (1966).
Krewson, C. F., W. E. Scott and J. S. Ard, U. S. Patent 3,157,676 (1964).
Krull, L., Fette Seifen, Anstrichmittel61, 223–227 (1959).
Kupchan, S. M., Y. Aynehchi, J. M. Cassady, A. T. McPhail, G. A. Sim, H. K. Schnoes and A. L. Burlingame, J. Am. Chem. Soc.88, 3674–3676 (1966).
Kupchan, S. M., R. W. Doskotch, P. Bollinger, A. T. McPhail, G. A. Sim and J. A. Saenz Renauld, Ibid.87, 5805–5806 (1965).
Kupchan, S. M., J. C. Hemingway, J. M. Cassady, J. R. Knox, A. T. McPhail and G. A. Sim, Ibid.89, 465–466 (1967).
Lindley, J., and T. Moore, “The Treasury of Botany,” Part 2, Longmans, Green, and Company, London, 1866, p. 1210.
Maerker, G., JAOCS42, 329–332 (1965).
Maerker, G., and E. T. Haeberer, Ibid.43, 97–100 (1966).
Maerker, G., E. T. Haeberer, and W. C. Ault, Ibid.,43, 100–104 (1966).
Maerker, G., E. T. Haeberer, and S. F. Herb, Ibid.43, 505–508 (1966).
Magne, F. C., Ibid.42, 332–336 (1965).
Majumdar, D. N., Ind. J. Pharm.5, 61–64 (1943).
Mallah, M. M. Hassen El, L. M. Souka and A. M. Gad, Fette, Seifen, Anstrichmittel68, 1028–1030 (1966).
Marasas, W. F., N. V. Riggs, E. B. Smalley and F. M. Strong, Abstracts, 154th National Meeting, American Chemical Society, Chicago, September 1967, p. Q70.
McConnell, W. V., and W. H. Moore, J. Org. Chem.28, 822–827 (1963).
Miwa, T. K., K. L. Mikolajczak, F. R. Earle and I. A. Wolff, Anal. Chem.32, 1739–1742 (1960).
a) Morris, L. J., “The Absolute Optical Configuration ofcis-12: 13-Epoxyoleic Acid fromVernonia Oil,” presented at the AOCS Meeting, St. Louis, May 1961; b) Morris, L. J., and D. M. Wharry, Lipids1, 41–46 (1966).
Morris, L. J., H. Hayes and R. T. Holman, JAOCS38, 316–321 (1961).
Morris, L. J., R. T. Holman, and K. Fontell, Ibid.37, 323–327 (1960).
Morris, L. J., R. T. Holman and K. Fontell, J. Lipid Res.2, 68–76 (1961).
Morris, L. J., M. O. Marshall and W. Kelly, Tetrahedron Letters No. 36, 4249–4253 (1966).
Mors, W. B., M. F. dos Santos F., H. J. Montiero, B. Gilbert and J. Pellegrino, Science157, 950–951 (1967).
Nicolet, B. H., and T. C. Poulter, J. Am. Chem. Soc.52, 1186–1195 (1930).
Pardo-Garcia Tapia, M. del Pilar, P. Artigas-Gimenez and J. Cabo-Torres, Medicamenta8, 263–264 (1952).
Powell, R. G., C. R. Smith Jr. and I. A. Wolff, JAOCS42, 165–169 (1965).
Powell, R. G., C. R. Smith Jr. and I. A. Wolff, Lipid2, 172–177 (1967).
Rackis, J. J., Federation Proc.24, 1488 (1965).
Radlove, S. B., R. V. Madrigal and R. Slutkin, JAOCS37, 570–571 (1960).
Rao, K. V., J. Ind. Chem. Soc.39, 749–752 (1962).
Riemenschneider, R. W., T. Zell and W. E. Scott, JAOCS43, 325–326 (1966).
Riser, G. R., J. J. Hunter, J. S. Ard and L. P. Witnauer, Ibid.39, 266–268 (1962).
Riser, G. R., J. J. Hunter, J. S. Ard and L. P. Witnauer, SPE Journal19, 729–734 (1963).
Riser, G. R., R. W. Riemenschneider and L. P. Witnauer, JAOCS43, 456–457 (1966).
Rosenfeld, R. S., M. C. Lebeau, S. Shulman and J. Seltzer, J. Chromatogr.7, 293–296 (1962).
Sampugna, J., R. G. Jensen, R. M. Parry Jr. and C. F. Krewson, JAOCS41, 132–133 (1964).
a) Scott, W. E., and C. F. Krewson, Ibid.42, 147–149 (1965);
b) Scott, W. E., and G. R. Riser, Ibid.43, 55–56 (1966).
Scott, W. E., and C. F. Krewson, Ibid.43, 466–468 (1966).
Scott, W. E., C. F. Krewson, F. E. Luddy and R. W. Riemenschneider, Ibid.40, 587–589 (1963).
Scott, W. E., C. F. Krewson and R. W. Riemenschneider, Chem. Ind. (London) 2038–2039 (1962).
Scott, W. E., C. F. Krewson and R. W. Riemenschneider, U. S. Patent 3,139,387 (1964).
Serck-Hanssen, K., and E. Stenhagen, Acta Chem. Scand.9, 866 (1955); Serck-Hanssen, K., Chem. and Ind. (London) 1554 (1958).
Smith, C. R., M. O. Bagley, R. L. Lohmar, C. A. Glass and I. A. Wolff, J. Org. Chem.25, 218–222 (1960).
Smith, C. R. Jr., K. F. Koch and I. A. Wolff, JAOCS36, 219–220 (1959).
Smith, C. R. Jr., K. F. Koch and I. A. Wolff, Chem. Ind. (London) 259–260 (1959).
Smith, C. R. Jr., M. C. Burnett, T. L. Wilson, R. L. Lohmar and I. A. Wolff, JAOCS37, 320–323 (1960).
Swern, D., T. W. Findley, G. N. Billen and J. T. Scanlan, Anal. Chem.19, 414–415 (1947).
Tallent, W. H., D. G. Cope, J. W. Hagemann, F. R. Earle and I. A. Wolff, Lipids1, 335–340 (1966).
Toubiana, R., and Gaudemer, A., Tetrahedron Letters No. 14, 1333–1336 (1957).
Tulloch, A. P., B. M. Craig and G. A. Ledingham, Can. J. Microbiol.5, 485–491 (1959).
Urbanski, J., and G. Kainz, Mikrochim. Acta 60–66 (1965).
Vanden Heuvel, W. J. A., C. C. Sweeley and E. C. Horning, Biochem. Biophys. Res. Commun.3, 33–36 (1960).
Vanden Heuvel, W. J. A., C. C. Sweeley and E. C. Horning, J. Am. Chem. Soc.82, 3481–3482 (1960).
Van Etten, C. H., R. W. Miller, I. A. Wolff and Q. Jones, J. Agr. and Food Chem.9, 79–82 (1961).
Vidyarthi, N. L., and M. V. Mallya, J. Ind. Chem. Soc.16, 479–480 (1939).
Didyarthi, N. L., Proc. 27th Ind. Sci. Congress, Section III, 79 (1940).
Vioque, E., L. J. Morris and R. T. Holman, JAOCS38, 489–492 (1961).
a) White, G. A., and J. R. Haun, “Vernonia Research Summary, 1963,” CR-30-64, New Crops Research Division, Crops Research Branch, USDA, Beltsville, Md., unpublished data; b) White, G. A., “Vernonia Research Summary, 1964,”, CR-44-65, New Crops Research Division, Crops Research Branch, USDA, Beltsville, Md., unpublished data; c) Higgins, J. J., and G. A. White, “Summary of 1965 Field Studies withVernonia anthelmintica andEuphorbia lagascae. Potential New Crop Source of Epoxy Acid,” New Crops Research Branch, USDA, Beltsville, Md., unpublished data; d) Higgins, J. J., “Vernonia anthelmintica: A Potential Seed Oil Source of Epoxy Acid. I. Phenology of Seed Yield,” submitted to Agronomy Journal; e) Higgins, J. J., and G. A. White, “Vernonia anthelmintica: A Potential Seed Oil Source of Epoxy Acid. II. Germination Studies,” submitted to Agronomy Journal; f) White, G. A., personal communication, 1967.
Wilson, T. L., C. R. Smith Jr., and K. L. Mikolajczak, JAOCS38, 696–699 (1961).
Wolff, I. A. Science154, 1140–1149 (1966).
Wu, Y. V., and H. A. Scheraga, Biochemistry1, 698–705 (1962); Ibid.1, 905–911 (1962).
Yokoyama, H., and M. J. White, J. Agr. and Food Chem.15, 693–696 (1967).
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E. Utiliz. Res. Dev. Div., ARS, USDA.
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Krewson, C.F. Naturally occurring epoxy oils1 . J Am Oil Chem Soc 45, 250–256 (1968). https://doi.org/10.1007/BF02652421
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DOI: https://doi.org/10.1007/BF02652421