Titanium tetrafluoride catalysis for the dehydrative conversion of diphenylmethanols to symmetric and unsymmetric ethers.

In contrast to the conversion of diphenylmethanol to the corresponding halides with an equivalent of titanium tetrachloride or -bromide, catalytic (50 mol%) titanium tetrafluoride converts benzhydrols in diethyl ether or dichloromethane to bis(benzhydryl) ethers within 0.5-1 h at room temperature. Cross ether formation with diphenylmethanols and primary aryl or aliphatic alcohols is achieved in the presence of 25 mol% TiF 4 in refluxing toluene as solvent. A tentative mechanism involving a carbocation intermediate has been proposed.