o-Acetaminophenols (2) reacted with Vilsmeier reagent under Meth-Cohn conditions to yield 2-formylpyrido [2, 1-b] benzoxazoles (5) unexpectedly besides the known compounds 2- (benzoxazol-2′-yl)-3-dimethylaminoacroleins (4). Refluxing 4 in acetic anhydride gave 4- formylpyrido [2, 1-b] benzoxazoles (6), an isomer of 5. Both 5a and 6a were structurally characterized by X-ray crystallography. A mechanism for the formation of 5 involving ...