AbstractA series of 2‐amino‐substituted 5,6‐benzo‐2H‐pyrans14, 2‐alkylidene‐5,6‐benzo‐2H‐pyrans15, and their dimers17are obtained, depending on the condition used, by the reaction of 2‐hydroxy‐benzaldehydes1with enamines9derived of (cyclo)aliphatic ketones. Compounds14, 15, and17can be transformed into 2‐alkyl‐benzopyrylium salts16or 2‐[1‐(2‐hydroxyphenyl)‐alken‐2‐yl]‐benzopyrylium salts23by treatment with mineral acids. With aromatic aldehydes or the Vilsmeier reagent the compounds14, 15, or17are transformed into deeply colored 2‐(aryl‐alkenyl)‐benzopyrylium perchlorates25or 2‐(2‐dialky