AbstractInvestigations of simple formoins such as 2,5‐bis(1,1‐dimethyl‐2‐phenylethyl)‐2,4‐dihydroxyfuran‐3(2H)‐one (17), benzoylformoin (18), p‐toluoylformoin (19), pivaloylformoin (20), and the 2,4‐dihydroxy‐2,5‐bis(heterocycl‐2‐yl)furan‐3‐ones 21−23 (heterocycle = furan, thiophene, selenophene) by NMR spectroscopy in DMSO showed the dihydroxyfuranone skeleton and not an enediol structure. The formoin 17 was oxidized to the corresponding tetraketone 10. The intermolecular double benzoin condensation of 1,4‐bis(2,2dimethyl‐3,4‐dioxobutyl)benzene (27) affords, in low yield, the bis(formoin) 29, and this could be oxidized to provide 2,2,2′,2′,7,7,7′,7′‐octamethyl[8.8]paracyclophan‐3,3′,4,4′5,5′6,6′‐octaone (9). The molecular structures of 17 and 29, the monohydrate of 10 (30), and also the dihydrate of 9 (31) are reported. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)