Summary: | Chromeno[2,3-<i>b</i>]pyridines are substances demanded in medicinal and material chemistry. <i>PASE</i> (pot, atom, and step economy) and in particular <i>one-pot</i> approaches are key green chemistry techniques that are applied for the synthesis of heterocyclic compounds. In this case, the <i>PASE</i> approach was extended with ‘component economy’, as solvent was used also as reactant (solvent-involved reaction). This approach was adopted for the <i>one-pot</i> synthesis of previously unknown <i>O</i>-substituted 5-alkoxy-5<i>H</i>-chromeno[2,3-<i>b</i>]pyridines via <i>two-step</i> transformation, namely the reaction of salicylaldehydes and malononitrile dimer, with the subsequent addition of alcohol. The mechanistic studies revealed the possibility of concurrent reaction. The studies aided in optimizing the reaction conditions for the best yields (77–93%). Thus, the <i>one-pot</i> reaction proceeds efficient and quickly, and the work-up procedure (only simple filtering) is very convenient. The structure of synthesized chromeno[2,3-<i>b</i>]pyridines was confirmed by 2D NMR spectroscopy.
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