Novel synthetic methods for phenoxathiins and phenothiazines by aryne reactions are disclosed. We found that phenoxathiins were efficiently prepared by the reaction between aryne intermediates and S-(2-hydroxyaryl) 4-toluenethiosulfonates. A synthetic method for phenothiazines was also developed by the reaction of arynes with S-(2-aminoaryl) 4-toluenethio sulfonates.