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Synthesis and Characterization of Phosphonates from Methyl Linoleate and Vegetable Oils

Grigor B. Bantchev, Bryan R. Moser, Rex E. Murray, Girma Biresaw, Stephen R. Hughes
Journal of the American Oil Chemists' Society 2016 v.93 no.12 pp. 1671-1682
byproducts, free radicals, gas chromatography-mass spectrometry, gel chromatography, lipids, nuclear magnetic resonance spectroscopy, phosphonates, phosphorus, soybean oil, stable isotopes, sunflower oil, temperature, transesterification, vegetable oil
Phosphonates were synthesized on a medium scale (~200 g) from three lipids—methyl linoleate (MeLin), high-oleic sunflower oil (HOSO) and soybean oil (SBO), and three dialkyl phosphites—methyl, ethyl and n-butyl, using a radical initiator. A staged addition of the lipid and the initiator was used to achieve good yields. Good results were observed with MeLin (94–99% conversions of the double bonds, as determined by NMR, and 83–99% isolated yields) and HOSO (99–100% NMR conversions, 87–96% isolated yields) using tert-butyl perbenzoate as the initiator. With SBO, benzoyl peroxide was used as the initiator, due to its capability to generate radicals at a higher rate at slightly lower temperatures, and thus to shorten the reaction time. Conversions of 91–93% (by NMR) and isolated yields of 80–94% were achieved. The progress of the reaction was monitored with GC–MS. The products were characterized using 1H, 13C and 31P NMR, IR and gel permeation chromatography. A prolonged reaction led to some transesterification between the carboxylic and phosphite ester groups. Conditions favoring higher reaction rates led to the formation of more oligomers and benzoate fatty ester byproducts. The benzoate fatty ester byproducts were formed by the attack of a benzoate radical on a double bond. The more double bonds that were present per lipid molecule, the more oligomers were formed: MeLin 2–8%, HOSO 3–9% and SBO 8–29%.