Cycloadditions. 24 Synthesis and Reactions of sec. N‐Aryl‐2,3‐butadienamides
The reaction of aryl isocyanates (1) with allenyl magnesium bromide (2) furnishes the sec. N‐aryl‐3‐butynamides (4), which tend to tautomerize to the 2,3‐butadienamides (5). Further heating of 5a–f (bearing benzoid nuclei) leads to decomposition, only 5g (bearing the naphthyl group) undergoes the expected intramolecular Diels‐Alder (IMDA) reaction, leading to the benzo‐tricycle (7g). By reaction of a second molecule isocyanate 1 the carbomoylation of the NH moiety of 5a, c and of 3g and 4g, resp. takes place. The thereby formed N‐aryl‐N‐butadienoyl ureas (9) either cyclize to furnish the the N‐carbamoyl‐2‐quinolones (10) or undergo the IMDA‐reaction leading to the tricyclic compounds (11). The N‐butadienoyl‐N‐(1‐naphthyl)ureas (12) only furnish the IMDA‐benzo‐tricycles (13).