Reaction of 3,6-diphenyl-1,2,4,5-tetrazine with cis,cis-1,5-cyclooctadiene: an attempt at preparing some dihydropyridazine derivatives

Abstract

The reaction of 3,6-diphenyl-1,2,4,5-tetrazine 1 with cis,cis-cycloocta-1,5-diene 7 has been studied with a view to preparing some interesting dihydropyridazine derivatives. Refluxing a mixture of 1 with excess of 7 in benzene solution for 8hr resulted in the formation of a mixture of products consisting of 1,4-diphenyl-10a-hydroperoxy-4a, 5,6,9,10,10a-hexahydrocycloocta[d]pyridazine (8, 27%) and 2,4a,5,6,8,10a,11,12-octahydro-1,4,7,10-tetraphenyldipyridazo[4,5-a:4',5'-e]cyclooctene ( However, when the reaction of 1 with 7 was carried out in refluxing benzene for nearly 40 hr, the products formed were a 14% yield of 8, a 17% yield of 9 and a 37% yield of 1,4-diphenyl-5,6,9,10-tetrahydrocycloocta[d]pyridazine (10). Neat heating of 1 with 7 around 150° for 10 hr, on the other hand, gave a 20% yield of 9, as the only isolable product. Thermolysis of 8 around 155° gave a mixture of products consisting of 2-oxocyclooct-5-enyl phenyl ketone N-benzoylhydrazone (15,30%) and 1H-3-phenyl-4,5,8,9-tetrahydrocycloocta[d]pyrazole (16, 22%). Nickel peroxide-oxidation of the adduct 9 gave a 67% yield of 1,4,7,10-tetraphenyldipyridazo[4,5-a:4',5'-e]cyclooctene (27). Acetylation of 9, on the other hand, gave a 70% yield of 2,3,8,9-tetraacetyl-2,3,5,6,8,9,11,12-octahydro-1,4,7,10-tetraphenyldipyridazo[4,5-a:4',5'-e]cyclooctene(28).