Tris(dimethylsilyl)methyllithium: A Reagent for the Synthesis of Vinylbis(silanes) Containing Si–H Functional Groups

Abstract

Reactions between a series of nonenolisable aldehydes and tris(dimethylsilyl)methyllithium, (HMe₂Si)₃CLi, are described. The Peterson reaction takes place readily to give vinylbis(silanes). Moreover, styrene and butyl acrylate 1:1 copolymer (P), prepared by use of α,α′-azobis(isobutyronitrile) (AIBN) as an initiator in toluene at 70 ± 1°C, was formylated via direct electophilic substitution by methyl dichloromethyl ether (Cl₂CHOMe) in the presence of tin(IV) chloride (SnCl₄) in nitrobenzene (PhNO₂) as solvent. The reaction of (HMe₂Si)₃CLi with formyl groups on the side chains of the copolymer led to new macromolecules bearing vinylbis(silane) functional groups.

Keywords:

• Functionalized copolymer
• Peterson reaction
• Si–H functional group
• tris(dimethylsilyl)methyllithium
• vinylbis(silanes)

ACKNOWLEDGMENT

We thank Dr. J. D. Smith for helpful comments.

Notes

^a Yields calculated by GC–mass spectroscopy.

^a All the molar compositions were calculated from the corresponding ¹H NMR spectra.