Alkoxychlorosilanes are scientifically and industrially important toward preparing silicone and silica as well as preparation of siloxane-based nanomaterials by stepwise reactions of Si−OR (R=alkyl) and Si−Cl groups. Intermolecular exchange of alkoxy and chloro groups between alkoxysilanes and chlorosilanes (functional group exchange reaction) provides an efficient and environmentally benign route to alkoxychlorosilanes. BiCl3 as a Lewis acid catalyst can promote the functional group exchange reactions more efficiently than conventional acid catalysts. Higher reactivity has been observed for chlorosilanes with smaller numbers of Si−CH3 groups and for alkoxysilanes with larger numbers of Si−CH3 groups. The reaction mechanism is proposed and selective syntheses of alkoxychlorosilanes are demonstrated. These findings also enable us to synthesize an organotrialkoxysilane with four different substituents.
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