Fused Supracyclopentadienyl Ligand Precursors.Synthesis,Structure,and Some Reactions of 1,3-Diphenylcyclopenta[l]phenanthrene-2-one,1,2,3-Triphenylcyclopenta[l]phenanthrene-2-ol,1-Chloro-1,2,3-triphenylcyclopenta[l]phenanthrene,1-Bromo-1,2,3-tripheny

摘要

The photochemical reaction of 1,3-diphenylcyclopenta[l]phenanthrene-2-one 5 (phencyclone) with oxygen in acetone leads to the formation of 1,2,3-trihydro-1,2,3-triphenylcyclo-penta[l]phenanthrene 7 (9,10-dibenzoyl-phenanthrene) along with a trace of the lactone 1,4-diphenylcyclo-3-pyran[l]phenanthrene-2-one 8.An independent synthesis of 8 was achieved by the reaction of 5 with FeCl_3 in CHCl_3.The treatment of 5 with phenyllithium yields 1,2,3-triphenylcyclopenta[l]phenanthrene-2-ol 9-OH in good yield.Subsequent reaction of 9-OH with SOCl_2 or SOBr_2 in pyridine leads to the formation of the halo-analogues 1-chloro-1,2,3-triphenylcyclopenta[l]phenanthrene 9-Cl and 1-bromo-1,2,3-triphenylcyclopenta[l]phenanthrene 9-Br,respectively.Treatment of 9-OH with HBr in acetic acid affords the rearranged product 1,1,3-triphenylcyclopenta[l]phenanthrene-2-one 10 with a trace of 9-Br.Treatment of 9-Cl or 9-Br with zinc in acetic acid affords 1,2,3-tri-phenyl-1H-cyclopenta[l]phenanthrene 9-H.9,10-Phenanthrenediylbis(phenyl)methanone 7 is formed in good yield upon treatment of 9-OH with HI in acetic acid followed by heating with H_2PO_4.Compounds 7,8,9-Cl,9-Br,and 10 have been structurally characterized using X-ray crystallography.