A New Entry to the C12H12 Energy Surface: Pyrolysis and Photolysis of trans-β-nona-2,4,6-trienyl>acrolein Tosylhydrazone Saltz

Article abstract of DOI:10.1021/jo00134a017

Thermal decomposition of the lithium salt of trans-β-nona-2,4,6-trienyl>acrolein tosylhydrazone (8) results in the formation of pentacyclo<6.4.0.0^2,12.0^3,7.0^4,11>dodeca-5,9-diene (12), exo- and endo-tricyclo<4.4.2.0^2,5>dodeca-3,7,9,11-tetraenes (9 and 10), 1,2-benzocycloocta-1,3,7-triene (11), and syn- and anti-9-(5-pyrazolyl)bicyclo<4.2.1>nona-2,4,7-trienes (14 and 13).The low-temperature photolysis of the sodium salt of tosylhydrazone 8 gives anti-9-(2-cyclopropen-1-yl)bicyclo<6.1.0>nona-2,4,6-triene (20), which affords pentacyclo<6.4.0.0^2,4.0^3,10.0^5,9>dodeca-6-11-diene (22) on thermolysis.Hydrocarbon 12 was formed in the photolysis of the sodium salt of trans-β-nona-2,4,7-trienyl>acrolein tosylhydrazone (15; available by thermal rearrangement of tosylhydrazone 8) as the sole C12H12 product.Structure determinations and mechanistic investigations are discussed.