Abstract The system Me 3 SiCl/Mg/hexamethylphosphorotriamide (HMPT) reacts with some di-or poly-chlorobenzenes leading directly to the corresponding di-or poly-trimethylsilyl derivatives (yields 70-85%). Reaction of trimethylsilyl chlorosulfonate with these compounds gives in a first step trimethylsilyl arylsulfonic esters, Ph (SiMe 3) SO 3 SiMe 3.