AbstractThe 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.