9-Hydroxyphenalenone is a planar multicyclic [beta]-keto-enol, which is synthesized via a Friedel-Crafts acylation followed by acid-catalyzed intramolecular Michael addition with the loss of a phenyl group in a one-pot reaction during a four-hour lab period. Tautomerization of the [beta]-keto-enol results in C[subscript 2v] symmetry on the NMR time scale, which simplifies the spectra and provides a unique structure for teaching 2D NMR spectroscopy. The [to the first power]H and [to the thirteenth power]C assignments can be made using 1D and 2D NMR techniques and data collection can be reduced to less than twenty minutes with optimized parameters. (Contains 2 figures, 1 scheme, 1 table and 1 note.)