Regioselective syntheses of 2- and 4-formylpyrido[2,1-b]benzoxazoles.
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 sequential chlorination, dimerization, intramolecular elimination of HCl to form the oxazole ring, formylation twice, and regioselective intramolecular nucleophilic cyclization to construct the pyridone ring is proposed.
Li
Ke-Lai
KL
College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, China.
Du
Zong-Bo
ZB
Guo
Can-Cheng
CC
Chen
Qing-Yun
QY