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The reactions of phloroglucinol with α,β-unsaturated dinitriles (or malononitrile and carbonyl compounds) lead to the formation of hitherto unknown 2,8-diamino-5-hydroxy-4H,10H-pyrano[2,3-f]chromene-3,9-dicarbonitriles. The reaction conditions and the structure of the products were studied in details.

&lt;strong&gt;Synthesis of 2,8-diamino-5-hydroxy-4&lt;em&gt;H&lt;/em&gt;,10&lt;em&gt;H&lt;/em&gt;-pyrano[2,3-&lt;em&gt;f&lt;/em&gt;]chromene-3,9-dicarbonitrile &lt;/strong&gt;