Abstract
A novel halogen-free synthesis of benzo-fused six-membered 1,4-heterocycles through
the chemistry of dialkyl carbonates is reported. Commercially available catechol,
2-aminophenol, and 2-aminothiophenol were reacted first with ethylene carbonate in
an autoclave to give O -hydroxyethyl, N -hydroxyethyl, and S -hydroxyethyl derivatives respectively, through a BAl 2 mechanism. Then 2-(2-hydroxyethoxy)phenol and 2-(2-hydroxyethylamino)phenol were
cyclized in excellent yields by reaction with dimethyl carbonate (DMC) and DABCO as
a bicyclic organic base to give the corresponding benzodioxine and benzoxazine derivative,
respectively. Moreover, 2-(2-aminophenylthio)ethanol afforded the benzothiazine derivative
in good yield by reaction with DMC with an excess of a strong base such as NaH. The
investigation on the cyclization reaction has highlighted that several equilibria
are involved leading to the formation of carbonate and carbamate intermediates through
BAc 2 mechanisms. Depending on the reaction conditions employed, these intermediates may
undergo either kinetic-controlled ring closure by a BAl 2 mechanism or by-product formation.
Key words heteroycles - cyclization reaction - green chemistry - alkylation - chemoselectivity
