Copper-Catalyzed Acetylation of Electron-Rich Phenols and Anilines

^◊These authors contributed equally.

Abstract

An approach has been developed for the copper-catalyzed acetylation of phenols and anilines with potassium thioacetate as an acetylating reagent. Although only electron-rich phenols and anilines are compatible with this protocol, the reaction can provide moderate to high yields under mild conditions. Compared with other acetylating reagents, the current reagent has certain advantages, such as its low cost, easy availability, stability, insensitivity to water or air, and ease of storage.

Key words

acetylation - phenols - anilines - copper catalysis - potassium thioacetate - butyl nitrite

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• 13 Acetylation of Anilines and Phenols with Potassium Thioacetate: General Procedure The appropriate aniline or phenol (0.5 mmol), KSAc (3.0 equiv), Cu(OAc)₂·H₂O (0.2 equiv), and MeCN (3 mL) were added to a screw-capped vial under air, and the vial was placed in a temperature-controlled oil bath at 80 °C. When the reaction was complete (TLC), the vial was removed from the oil bath and allowed to cool to r.t. The solution was filtered through a short column of silica gel that was washed with EtOAc. The filtrate was concentrated under reduced pressure to give a crude product that was purified by flash column chromatography (silica gel, PE–EtOAc). 2-Naphthyl Acetate (3a) Creamy-white solid powder; yield: 86.5 mg (93%); mp 68–70 °C. ¹H NMR (300 MHz, CDCl₃): δ = 7.91–7.84 (m, 3 H), 7.61 (s, 1 H), 7.52 (t, J = 3.9 Hz, 2 H), 7.29 (t, J = 7.2 Hz, 1 H), 2.40 (s, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 169.8, 148.4, 133.8, 131.6, 129.5, 127.9, 127.7, 126.7, 125.8, 121.2, 118.6, 21.3.