SYNTHESIS AND REACTIONS OF HIGHLY STERICALLY HINDERED ORGANOSILICON COMPOUNDS OF THE TYPE (ME3SI)(3)CSI(C6H4OME-P)(2)X

Reaction of TsiLi (Tsi = (Me3Si)(3)C) with (p-MeOC6H4)(2)SiF2 gave Tsi Si(C6H4OMe-p)(2)F, which was treated with LiAlH4 to give (Me3Si)(3)CSi (C6H4OMe-p)(2)H. Treatment of the latter with ICl in the presence of a large excess of Me3SiC6H4OMe-p gave (Me3Si)(3)CSi(C6H4OMe-p)(2)Cl rat her than the expected (Me3Si)(3)CSi(C6H4OMe-p)(2)I. Use of Br-2 in pla ce of ICl gave (Me3Si)(3)CSi(C6H4OMe-p)(2)Br. The fluoride (Me3Si)(3)C Si(C6H4OMe-p)(2)F was found to react with NaOMe/MeOH and NaOEt/EtOH, t o give (Me3Si)(2)CHSi(C6H4OMe-p)(2)OMe and (Me3Si)(2)CHSi(C6H4OMe-p)(2 )OEt, respectively, and secondary products formed from them. Only seco ndary products were observed from the corresponding (prolonged) reacti ons in NaOPri/(PrOH)-O-i, and KOBut/(BuOH)-O-t. The diol (p-MeOC6H4)(2 )Si(OH)(2) was made by hydrolysis of (p-MeOC6H4)(2)SiCl2. (C) 1997 Els evier Science S.A.