REACTION OF 5-AMINOBENZOTRIAZOLES WITH METHYL PROPIOLATE - FORMATION OF TRIAZOLO[4,5-F]QUINOLINES AND RELATED-COMPOUNDS - UNUSUAL PRODUCTS IN THE MICHAEL ADDITION-REACTION OF 2-METHYL-2H-5-AMINOBENZOTRIAZOLE

Reaction of 5-aminobenzotriazoles (1b-d) with methyl propiolate gives (Z/E)-3-[1(2)(3)-methyl(benzotriazol-5-yl)]aminomonopropenoates (5b-d) and (E)-3-[1(2)(3)-methyl(benzotriazol-5-yl)]aminobispropenoates (6b-d), while in the case of la addition took place on the nitrogen of the triazole ring to give mixtures of (E)-3-(5-aminobenzotriazol-1(2)(3)-yl)propenoates (2,3,4). Mono- (5b-d) and bis-adducts (6b-d) underwent further reaction which also led to the isolation of triazolo[4,5-f]quinolines, of a triazolo[4,5-f]carbostyril and 1-[benzotriazol-5-yl]-2-pyridones. Formation of these compounds depends on the reaction conditions: the solvent employed and the temperature. Thermal cyclization of Michael adduct (Z/E)-(5c) gave triazoloquinolinone (9c) and the rearranged product (13) in various ratio depending on the concentration of Dowtherm used.