Highly regioselective heterocyclization reactions of 1H-1,2,4-triazole-3-thiols with chloroacetylenephosphonates

Abstract

1-Chloroacetylene-2-phosphonates react with 1H-1,2,4-triazole-3-thiols in anhydrous acetonitrile with high regioselectivity to form the fused heterocycles, 6-(dialkoxyphosphoryl)-3H-thiazolo[3,2-b][1,2,4]triazol-7-ylium chlorides 1–5. A significant difference from the previously known reactions of binucleophiles with haloacetylenes is the involvement of both acetylenic carbon atoms in the heterocycle formation. A reaction mechanism is hypothesized that assumes the formation of a sulfenium cation at the acetylene C-1 atom followed by attack of the C-2 atom by the ring N-2 atom. Compounds 1–5 easily lose one alkyl group from the dialkoxyphosphoryl fragment to form zwitterions (e.g., 6–8) which further can be transformed into inner salts 9 and 10 when heated with concentrated hydrochloric acid.