Syntheses and NMR,MS and X‐ray investigations of homoadamantane‐fused pyridopyrimidinones

The reactions of ethyl 5‐oxotricyclo[4.3.1.1^3,8]undecane‐4‐carboxylate (2) with methyl‐substituted 2‐aminopyridines in polyphosphoric acid (PPA) gave two products, linearly‐condensed pyridopyrimidinones 4a‐c and 2‐pyridylcarboxamides 5a‐c , whereas the reactions with amino, hydroxy and nitro derivatives of 2‐aminopyridine furnished only linearly‐condensed pyridopyrimidinones (4g‐j). Use of a mixture of PPA and phosphorus oxychloride as solvent afforded both linearly‐ (4a‐c,e,f) and angularly‐condensed (6a–c,e,f) pyridopyrimidinones. In toluene, with p‐toluenesulfonic acid as catalyst, 2‐pyridylcarboxamides 5a‐f were obtained. In a mixture of PPA and phosphorus oxychloride at 80–120 °C, 5a‐f yielded angularly‐condensed pyridopyrimidinones 6a‐f. All the products exhibited characteristic features, as determined by NMR and electron ionization mass spectrometry and X‐ray crystallography.