Regioselective Syntheses of 2- and 4-Formylpyrido[2,1-b]benzoxazoles

摘要

o-Acetaminophenols (2) reacted with Vilsmeier reagent under Meth-Cohn conditions to yield 2-formylpy-rido[2,1-Mbenzoxazoles (5) unexpectedly besides the known compounds 2-(benzoxazol-2'-y1)-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 mechanismfor the formation of 5 involving sequential chlorination, dimerization, intramolecular elimination of HClto form the oxazole ring, formylation twice, and regioselective intramolecular nucleophilic cyclization toconstruct the pyridone ring is proposed.