One‐Step Synthesis of Siloxanes from the Direct Process Disilane Residue

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The well-established Müller-Rochow Direct Process for the chloromethylsilane synthesis produces a disilane residue (DPR) consisting of compounds Men Si2 Cl6-n (n=1-6) in thousands of tons annually. Technologically, much effort is made to retransfer the disilanes into monosilanes suitable for introduction into the siloxane production chain for increase in economic value. Here, we report on a single step reaction to directly form cyclic, linear, and cage-like siloxanes upon treatment of the DPR with a 5 m HCl in Et2 O solution at about 120 °C for 60 h. For simplification of the Si-Si bond cleavage and aiming on product selectivity the grade of methylation at the silicon backbone is increased to n≥4. Moreover, the HCl/Et2 O reagent is also suitable to produce siloxanes from the corresponding monosilanes under comparable conditions.