Synthesis of Anthraquinone Derivatives: Tandem Diels-Alder-Decarboxyl­ation-Oxidation Reaction of 3-Hydroxy-2-pyrone with 1,4-Naphthoquinone

Abstract

In the presence of triethylamine, the Diels-Alder reaction of 3-hydroxy-2-pyrones with 1,4-naphthoquinones by a decarboxylation-oxidation process gave anthraquinone derivatives in good to excellent yields.

Key words

3-hydroxy-2-pyrone - tandem reactions - Diels-Alder reactions - anthraquinone - oxidations

References and Notes

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12

Without triethylamine, the reaction of 1a and 2a gave only traces of desired compound 4a.

14

Anthraquinone 4c; Typical Procedure. To a stirred solution of 1,4-naphthoquinone 2a (72 mg, 0.46 mmol) and 2-pyrone 1c (50 mg, 0.23 mmol) in toluene (5 mL) was added Et₃N (2 mg, 0.02 mmol) and the reaction mixture was heated to reflux for 2 h. Then the reaction mixture was allowed to cool to r.t. After evaporation of the solvent, the crude product was purified by column chromatography (hexane-EtOAc, 50:1) to give anthraquinone 4c (70 mg, 93%) as an orange solid; mp 210-212 °C. IR (neat): 1662, 1630, 1591, 1424, 1349, 1285, 1217, 1126, 1017, 747, 708 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 7.07 (d, J = 8.1 Hz, 1 H), 7.47-7.49 (m, 3 H), 7.57-7.61 (m, 2 H), 7.67 (d, J = 8.1 Hz, 1 H), 7.80-7.85 (m, 2 H), 8.27-8.34 (m, 2 H), 13.3 (br, 1 H). Anal. Calcd for C₂₀H₁₂O₃S: C, 72.27; H, 3.64. Found: C, 72.48; H, 3.66.