Abstract
The addition of dialkyl phosphite (methyl, ethyl and n-butyl) to methyl linoleate (MeLin) double bonds was investigated. The reaction proved to be more challenging than the analogous reaction with methyl oleate (MeOl), due to inhibition of the radical reaction by the bis-allylic hydrogens of MeLin and the lower reactivity of MeLin double bonds. However, we demonstrated that this self-inhibition problem can be solved by simply keeping the MeLin reagent at low concentrations, while keeping the dialkyl phosphite at high concentrations. For optimization of the reaction, four different radical initiators were investigated: dilauroyl peroxide (LP), 2,2′-azobis(2-methylpropionitrile) (AIBN), tert-butyl perbenzoate (t-BP), and tert-butyl peroxide (TOOT). The initiators were used at temperatures that provided a half-life of 10 h: 64, 64, 104, and 125 °C respectively for LP, AIBN, t-BP, and TOOT. The tests showed the reaction to be faster at higher temperatures, but transesterification of the ester groups was also observed at elevated temperatures. t-BP was chosen as an optimal initiator for carrying the reaction. The apparent order of reactivity of the dimethyl, diethyl and di-n-butyl phosphites (Me >Et >n-Bu) towards MeLin was due to differences in their molar volumes. When the concentrations of dialkyl phosphite were kept the same, the order reversed (n-Bu > Et~Me). GC–MS spectra of the resulting phosphonates are reported and the main fragments assigned.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Biresaw G, Bantchev GB (2013) Tribological properties of biobased ester phosphonates. J Am Oil Chem Soc 90(6):891–902
Erickson FL, Anderson RE, Landis PS (1994) Vegetable oil derivatives as lubricant additives. US Patent 5,282,989
Swern D, Sasin R (1963) Trialkyl 9(10)-phosphonostearates as plasticizer for vinyl chloride polymers. US Patent 3,101,325
Mod RR, Harris JA, Arthur Jr., JC, Magne FC, Sumrell M, Novak AF (1977) Process for the preparation of phosphonated N,N-disubstituted fatty amides. US Patent 4,008,137
Sharma BK, Doll KM, Pereira MSC, Santos GFN, Suarez PAZ, Erhan SZ (2012) Production of phosphorus-containing oleochemicals through an epoxide route. Intern J Sustain Eng 5(3):280–285
Guo Y, Hardesty JH, Mannari VM, Massingill JL Jr (2007) Hydrolysis of epoxidized soybean oil in the presence of phosphoric acid. J Am Oil Chem Soc 84(10):929–935
Hamilton LA, Williams RH (1960) Synthesis of compounds having a carbon-phosphorus linkage. US Patent 2,957,931
Swern D, Sasin R (1961) Trialkyl 9(10)-phosphonostearates. US Patent 2,988,558
Sasin R, De Mauriac RA, Leopold EJ, Gordon HB, Sasin GS (1965) Phosphorus derivatives of fatty acids. The addition of dialkyl phosphonates to unsaturated acids and the synthesis of some 11-dialkylphosphonoundecanoamides. J Am Oil Chem Soc 42:134–136
Bantchev GB, Biresaw G, Vermillion K, Appell M (2013) Synthesis and spectral characterization of methyl 9(10)-dialkylphosphonostearates. Spectrochim Acta Part A Mol Biomol Spectrosc 110:81–91
Sanchez J, Myers TN (1995) Free-radical initiators. In: Kirk RE, Othmer DF, Kroschwitz JI, Howe-Grant M (eds) Kirk-othmer encyclopedia of chemical technology, vol 16. Wiley, New York, pp 431–460
Stiles AR, Vaughan WE, Rust FF (1958) The preparation of dialkyl alkylphosphonates by addition of dialkyl phosphites to olefins. J Am Chem Soc 80(3):714–716
Ferreri C, Costantino C, Perrotta L, Landi L, Mulazzani QG, Chatgilialoglu C (2001) Cis-trans isomerization of polyunsaturated fatty acid residues in phospholipids catalyzed by thiyl radicals. J Am Chem Soc 123(19):4459–4468
Dean JA (1999) “Table 2.2.H. Kinetics” in Lange’s Handbook of Chemistry 15th edn. McGraw-Hill, New York
Gadagkar SR, Call GB (2015) Computational tools for fitting the Hill equation to dose—response curves. J Pharmacol Toxicol Methods 71:68–76
Brown AM (2001) A step-by-step guide to non-linear regression analysis of experimental data using a Microsoft Excel spreadsheet. Comput Methods Programs Biomed 65:191–200
Press WH, Teukolsky SA, Vetterling WT, Flannery BP (2007) Modelling of data. In: Numerical Recipes, 3rd edn, Ch. 15. Cambridge University Press, Cambridge
Bantchev GB, Kenar JA, Biresaw G, Han MG (2009) Free radical addition of butanethiol to vegetable oil double bonds. J Agric Food Chem 57(4):1282–1290
Najder LE (1964) Thin Film Evaporation. Ind Eng Chem 56(2):26–30
Acknowledgments
We thank Mr. Benjamin Lowery for help with the GC–MS, and Dr. Kristen Woods and Ms. Erin Walter for technical support.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Funding
This work was a part of the in-house research of the Agricultural Research Service of the United States Department of Agriculture.
Conflict of interest
The authors declare that they have no conflict of interest.
Electronic supplementary material
Below is the link to the electronic supplementary material.
About this article
Cite this article
Bantchev, G.B., Biresaw, G., Palmquist, D.E. et al. Radical-Initiated Reaction of Methyl Linoleate with Dialkyl Phosphites. J Am Oil Chem Soc 93, 859–868 (2016). https://doi.org/10.1007/s11746-016-2820-y
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11746-016-2820-y