Palladium-catalyzed formation and reactions of iodo- and bromosiloxane intermediates

Polysiloxanes are useful materials because of their functionality, such as high thermal stability, electrical resistance, and hydrophobicity. In this regard, we studied palladium-catalyzed formation of iodo- and bromopolysiloxanes from two types of hydrosiloxanes, α,ω-dihydropoly(dimethylsiloxane) (1) and cyclotetra(hydromethylsiloxane) (2), and their reactions. Treatment of 1 with mixtures of cyclic ethers or lactones and MeI or allylBr in the presence of a catalytic amount of PdCl2 gave the corresponding α,ω-bis(haloalkoxy and haloalkanoyloxy)poly(dimethylsiloxane)s in good yields, via iodo- and bromopoly(dimethylsiloxane) intermediates. Transformation of the iodobutoxy-terminal units in the resulting poly(dimethylsiloxane) into aminoalkoxy groups was examined. The formation of α,ω-diiodo- and dibromopoly(dimethylsiloxane)s from 1 was confirmed by spectrometric analysis as well as by quenching experiments with ethanol. A reaction of α,ω-dibromopoly(dimethylsiloxane) with 2,5-dilithiothiophene gave a polydimethylsiloxane-thiophene alternating polymer. Similar palladium-catalyzed reactions of 2 with THF/MeI, THF/allylBr, and δ-valerolactone/allylBr afforded cyclo-(halobutoxy- and bromobutanoyloxymethylsiloxane)s in moderate yields. This would provide a new strategy for the introduction of various substituents to the terminal positions of linear polysiloxane and to the cyclosiloxane core.

The PdCl2-catalyzed formation and reactions of iodo- and bromosiloxane intermediates form α,ω-dihydropoly(dimethylsiloxane) and cyclotetra(hydromethylsiloxane) were studied. The in-situ generated iodo- and bromosiloxane intermediates readily reacted with cyclic ethers and lactones, leading to haloalkoxy- and haloalkanoyloxy-terminated polysiloxanes and –substituted cyclosiloxanes.Figure optionsDownload as PowerPoint slideHighlights
► We studied the PdCl2-catalyzed formation of iodo- and bromosiloxanes.
► The iodo- and bromosiloxanes readily reacted with cyclic ethers and lactones.
► A potential application of α,ω-dibromopolysiloxane as a mocromonomer was explored.