Synthesis of 2,4-disubstituted thiophenols and solid state structures of thiocarbamate precursors

A series of thiophenols with different ortho-substituents, 2,4-dimethylthiophenol, 2-tert-butyl-4- methylthiophenol, and 2-(1-adamantyl)-4-methylthiophenol, which display varying degrees of steric hindrance on the 2- position, was prepared from the corresponding phenols. Initial deprotonation of the phenols was achieved with NaH in dimethoxyethane, followed by treatment with N,N-dimethylthiocarbamoyl chloride, to obtain the O-arylthiocarbamates. Thermolysis of the latter compounds resulted in rearrangement, which yields the desired S-arylthiocarbamates. Finally, reduction of the S-arylthiocarbamates with LiAlH4 in THF, followed by acidic workup, allowed the isolation of the thiophenols. All products were characterized by spectroscopic techniques, and in the case of some of the thiocarbamates the solid state structures were determined by single-crystal X-ray diffraction.