Propargyloxy- and allenyloxymethylferrocenes: Synthesis and oligomerization

•An efficient method for synthesis of propargyloxymethylferrocene has been elaborated.•Previously unknown allenyloxymethylferrocene has been synthesized in 80% yield.•Novel oligomers with polyene chain and pendant ferrocenyl moieties were synthesized.•The oligomers exhibit semiconducting and paramagnetic properties.

Propargyloxymethylferrocene has been synthesized by the modified reaction of available N,N-dimethylaminomethylferrocene with propargyl alcohol in the presence of dichloroethane and NaOH, the yield reaching 99.6%. The rapid prototropic isomerization of propargyloxymethylferrocene in the superbase system t-BuOK/DMSO (room temperature, 4 min) leads to previously unknown allenyloxymethylferrocene in 80% yield. Preliminary cationic and radical polymerizations of both monomers have been studied and novel oligomers with the polyene chain and pendant ferrocenyl moieties containing soluble and insoluble fractions have been synthesized in 83–88% total yield. All the oligomers exhibit semiconducting and paramagnetic properties and stable up to 300–340 °C.

Graphical abstractFormation and polymerization of propargyloxymethyl- and allenyloxymethylferrocenes.Figure optionsDownload full-size imageDownload as PowerPoint slide