Symmetrically hindered methylphenols 1 react smoothly with NBS to form transient intermediates, p-benzoquinone methides (BM), which can be further processed to give hydroxybenzaldehydes in the presence of DMSO. This reaction is initiated by the formation of the phenoxy radical, followed by disproportionation to afford BM. None of the side-chain-brominated product is observed. The existence of BM is supported by the following observations: the formation of BM in solution can be monitored by GC and GC-MS; the electrophilic methine part participates in electrophilic aromatic substitution with anisoles to give hydroxybenzylated products 15; and the double bond character of the exocyclic methine plays a role in [4 + 2] cycloaddition with diene to afford Diels-Alder adducts. In contrast, unsymmetrically hindered or simple methylphenol (p-cresol) with NBS gives the nuclear brominated products, as usual. The energies of symmetrically hindered BMs, unsymmetrically hindered BM, and simple BM were calculated using density functional theories. Relative stabilization energies calculated at the B3LYP/6-31G//B3LYP/6-31G level by an isodesmic equation are enhanced 3-6 kcal/mol for symmetrically hindered BMs.

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