Abstract: Benzenethiol, toluene-4-thio1, and 3, 5-dimethylbenzenethiol are doubly lithiated (on sulfur and on carbon) by n-butyllithium in tetramethylethylenediamine. C-Lithiation occurs ortho to the thiol group, and subsequent treatment with electrophiles provides a convenient approach to ortho-substituted arenethiol derivatives. The reactions with tetraisopropylthiuram disulfide provide direct access to the corresponding o-phenylene ...