Epoxy Fatty Acids

The Author: Gerhard Knothe, National Center for Agricultural Utilization Research, Agricultural Research Service, U.S. Department of Agriculture, Peoria, IL, USA.

Most epoxy compounds have signals for the protons attached to the epoxidized carbons at 2.7 ppm for cis and 2.45 ppm for trans (Gunstone and Jacobsberg, 1972). More details are given in Table 1.

Table 1. Chemical shifts in methyl epoxyoctadecanoates (Gunstone and Jacobsberg, 1972). Solvent, carbon tetrachloride (CCl4). 220MHz. Recalculated from τ values given in the original literature.
Isomer (position of epoxy group)CH3—formula—CH2—COOMe
 cistranscistranscistrans
2,3 0.88 0.88 3.30, 2.99 2.99 - -
3,4 0.87 0.88 3.16, 2.85 2.56, 2.86 2.36, 2.60 2.30, 2.58
5,6 0.88 0.88-0.91 2.71 2.45-2.49 2.31 2.21-2.28
6,7-13,14 0.88-0.93 2.68-2.70 2.20-2.25
14,15 0.97 0.94 2.68 2.46 2.20 2.20
15,16 1.01 0.95 2.67 2.45 2.20 2.20
16,17 1.21 1.17 2.69, 2.83 2.52, 2.54 2.20 2.20
17,18 - N/A 2.26, 2.53, 2.72 N/A 2.20 N/A
 

 

In deuterobenzene (C6D6) (400 MHz), the shifts of the protons at C-9 and C-10 of methyl 9,10-epoxyoctadecanoate were reported at 2.97-3.02 as a broad singlet (Piazza et al., 2002).

Epoxyoctadecenoic, epoxyoctadecynoic and diepoxyoctadecanoic esters (220 MHz; CCl4) were also analysed (Gunstone and Schuler, 1975). In diepoxides, the signals of the protons on the epoxy carbons of diepoxystearates are found at about 2.70-2.95 ppm (cis epoxides) and 2.50-2.70 ppm (trans). Diepoxides separated by only one CH2 gave two signals caused by the inner and outer pairs of CH protons, cis,cis for example at 2.91 and 2.79 ppm (9, 12) or 2.93 and 2.81 (6, 9) as well as trans,trans (2.65 and 2.52). Similar results were obtained for methyl 9,10-12,13-diepoxy octadecanoate in C6D6, for which multiplets at 2.92-3.00 ppm (protons at C9 and C13) and 3.14-3.21 ppm (protons at C10 and C11) were reported besides a triplet at 1.82-1.87 ppm for the protons at C11 (Piazza et al., 2002). Four signals are observed for cis/trans epoxides (2.91, 2.78, 2.66, 2.55; 2.93, 2.78, 2.66, 2.55) (Gunstone and Schuler, 1975). This separation is not apparent when the epoxy groups are separated by more than one CH2 group but a slight downfield shift to 2.76 and 2.77 (two methylenes), 2.73 and 2.75 (three methylenes), 2.73 (four methylenes) and 2.72 (five methylenes). These shifts are less significant in unsaturated epoxides with the epoxy protons causing signals at 2.69-2.75 (cis) and 2.49-2.50 (trans; one methylene only); see below.

Unsaturated Epoxy Compounds

1H-NMR data have also been reported for some unsaturated epoxy compounds. Table 2 contains characteristic data for such fatty compounds.

Table 2. Signals in the 1H-NMR of unsaturated methyl epoxyoctadecenoates
Double/ triple bondEpoxy—CH=CH—formula  
9(Z)a Z-12,13 5.33 (m, H-10); 5.43 (m, H-9) 2.82 (m, H-12 and H-13) 2.10, 2.27 (both m, each 1H of H-11) 1.44 (m, H-14)
9(Z)b E-11,12 5.64-5.73 (m, H-9);
5.00-5.08 (m, H-10)		 3.31-3.35 (m, H-11);
2.79-2.83 (m, H-12)		   2.15-2.25 (H-8);
1.52-1.57 (H-13)
11(E)b Z-9,10 5.92 (dt, H-12);
5.25-5.34 (m, H-11)		 3.36 (q, H-10); 3.01-3.09 (m, H-9)   2.01-2.12 (m, H-13),
1.46-1.52 (m, H-7 and H-8)
9a,c Z-11,12 - 2.95 (m, H-12); 3.41 (d, H-11)   2.21 (t<, H-8)
 
aMethyl ester of vernolic acid (methyl vernolate). Reference: Fürmeier and Metzger, 2003.
bReference: Lie Ken Jie et al., 2003.
cReference: Lie Ken Jie and Alam, 2001

 

Literature:

  • Fürmeier, S.. and Metzger, J.O. Fat-derived aziridines and their n-substituted derivatives: biologically active compounds based on renewable raw materials. Eur. J. Org. Chem., 649-659 (2003).
  • Gunstone, F.D. and Jacobsberg, F.R. The preparation and properties of the complete series of methyl epoxyoctadecanoates. Chem. Phys. Lipids, 9, 26-34 (1972).
  • Gunstone, F.D. and Schuler, H.R. Fatty acids, Part 46. PMR spectra of several epoxyoctadecenoic, epoxyoctadecynoic, and diepoxyoctadecanoic esters. Chem. Phys. Lipids, 15, 189-197 (1975).
  • Kannan, R., Subbaram, M.R. and Achaya, K.T. NMR studies of some oxygenated. halogenated, and sulphur-containing fatty acids and their derivatives. Fette Seifen Anstrichm., 76, 344-350 (1974).
  • Lie Ken Jie, M.S.F. and Alam, M.S. Novel azido fatty acid ester derivatives from conjugated C18 enynoate. Chem. Phys. Lipids, 111, 29-35 (2001).
  • Lie Ken Jie, M.S.F., Lam, C.N.W., Ho, J.C.M. and Lau, M.M.L. Epoxidation of a conjugated linoleic acid isomer. Eur. J. Lipid Sci. Technol., 105, 391-396 (2003).
  • Piazza, G.J., Nuňez, A. and Foglia, T.A. Epoxidation of fatty acids, fatty methyl esters, and alkenes by immobilized oat seed peroxygenase. J. Mol. Catal. B: Enzym., 21, 143-151 (2003).

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