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-triphenylcyclopenta[l]phenanthrene, and 1,2,3-Triphenyl-1H-cyclopenta[l]phenanthrene

Glen D. Dennis; David Edwards-Davis; Leslie D. Field; Anthony F. Masters; Thomas Maschmeyer; Antony J. Ward; Irmi E. Buys; Peter Turner

doi:10.1071/CH05172

RESEARCH ARTICLE

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-triphenylcyclopenta[l]phenanthrene, and 1,2,3-Triphenyl-1H-cyclopenta[l]phenanthrene

Glen D. Dennis ^A , David Edwards-Davis ^A , Leslie D. Field ^A ^B , Anthony F. Masters ^A ^C , Thomas Maschmeyer ^A , Antony J. Ward ^A , Irmi E. Buys ^A and Peter Turner ^A

+ Author Affiliations

- Author Affiliations

^A Centre for Heavy Metals Research and School of Chemistry, University of Sydney, Sydney NSW 2006, Australia.

^B University of New South Wales, Kensington NSW 2052, Australia.

^C Corresponding author. Email: a.masters@chem.usyd.edu.au

Australian Journal of Chemistry 59(2) 135-146 https://doi.org/10.1071/CH05172
Submitted: 12 July 2005 Accepted: 4 January 2006 Published: 7 March 2006

Abstract

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-dibenzoylphenanthrene) 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 FeCl₃ in CHCl₃. 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 SOCl₂ or SOBr₂ 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 H₂PO₄. Compounds 7, 8, 9-Cl, 9-Br, and 10 have been structurally characterized using X-ray crystallography.

Acknowledgement

We thank the Australian Research Council for financial support.

References

^* A referee has commented (and we concur) that difficulties with the original synthesis can be caused by experimental technique — the phenanthrenequinone purity and/or delays between synthesis steps.

^† Impurities (including a hydrate) have been noted by several authors.^[^25–28^] We find that reaction in refluxing propanol initially gives the cis isomer of 1,3-dihydro-1,3-diphenylcyclopenta[l]phenanthrene-2-one 6 (dihydrophencyclone), which isomerizes to the trans isomer. Sonntag et al.^[²⁸^] classify the reaction as an ‘isomerization–cyclization’ rather than a reduction.

Abstract

Acknowledgement

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