Synthesis and reactions of 1,3-dicarbonyl-substituted troponoids: Conversion to tropolones having an isoxazole or a pyrazole ring

3-Acetyltropolone ( 1 ) was treated with diethyl oxalate in the presence of sodium ethoxide to afford 3-(2-ethoxalyl-1-oxoethyl)tropolone ( 2 ) as a minor product and its cyclized 2-ethoxycarbonyl-4,9-dihydrocyclohetpa[b]pyran-4,9-dione ( 3 ) as the major one. The former was readily converted to the latter. Then, as a stable synthon bearing a 1,3-dicarbonyl group, 2-(2-ethoxalyl-1-oxoethyl)-7-methylaminotropone ( 5 ) was prepared. The reactions of compound 5 with hydroxylamine, hydrazine, and methylhydrazine were carried out to give troponoids possessing an isoxazole or a pyrazole ring. The parent compounds, 3-(3-pyrazolyl)tropolone ( 13 ) and 3-(1-methylpyrazol-3-yl)tropolone ( 21 ), were obtained via hydrolysis and decarboxylation. Similarly, 2-ethoxycarbonyl-4,9-dihydrocyclohepta[b]pyran-4,9-dione ( 3 ) reacted with hydroxylamine, hydrazine, and methylhydrazine to yield troponoids possessing a heterocyclic ring.