Aromatic Halogenation Using N-Halosuccinimide and PhSSiMe or PhSSPh.

We developed a mild aromatic halogenation reaction using a combination of N-halosuccinimide and PhSSiMe or PhSSPh. Less reactive aromatic compounds, such as methyl 4-methoxybenzoate, were brominated with PhSSiMe or PhSSPh and N-bromosuccinimide in high yields. No reaction was observed in the absence of PhSSiMe or PhSSPh.

Transformation of Methylene Acetals to Bromoformates with a Combination of Trimethyl(phenylthio)silane and N-Bromosuccinimide.

A novel transformation reaction of methylene acetals, using a combination of trimethyl(phenylthio)silane (PhSTMS) and N-bromosuccinimide (NBS) under mild reaction conditions, is described. Various methylene acetals were converted to their corresponding bromoformates in good to high yields. Under the given conditions, the reaction proceeded via a radical pathway.