Abstract
δ-Eicosanolactone and δ-docosanolactone were synthesized directly from the triacylglycerides of meadowfoam (Limnanthes) oil. Perchloric and sulfuric acids were used in stoichiometric quantities (0.5–4.0 mol equiv) to cyclize triglyceride to δ-lactone. When the reactions were run in the absence of solvent at 40°C, δ-lactone yields ranged from 17–75% where δ/γ ratios ranged from 6∶1 to 10.4.∶1. Sulfuric and perchloric acids gave similar yields for their individually optimized reactions. Perchloric acid-catalyzed reactions required less acid to produce similar amounts of δ-lactone (HClO4 at 2.0 mol equiv gave 73% yield vs. H2SO4, which gave 75% yield at 2.5 mol equiv). The use of polar nonparticipating solvents during the reaction had little impact on δ-lactone formation or δ/γ ratio. Higher perchoric acid concentrations provided higher δ-lactone yields with δ/γ ratios remaining nearly constant. The effect of sulfuric acid on δ-lactone yield and δ/γ ratio was more direct; higher acid concentration improved, both. Both crystallization and short path distillation improved δ-lactone quality but short path distillation gave, higher recovered yields. The δ-lactones were converted to their corresponding 5-hydroxy acids in the same reaction vessel, separated, and cyclized back to δ-lactones upon heating under vacuum. This provided a convenient method for δ-lactone purification.
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Isbell, T.A., Cermak, S.C. Synthesis of δ-eicosanolactone and δ-docosanolactone directly from meadowfoam oil. J Amer Oil Chem Soc 78, 527–531 (2001). https://doi.org/10.1007/s11746-001-0297-9
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DOI: https://doi.org/10.1007/s11746-001-0297-9