Magnetic Graphitic Carbon Nitride-Catalyzed Highly Efficient Construction of Functionalized 4H-Pyrans

Abstract

A high-yielding, practical, efficient, and environmentally benign one-pot multicomponent synthesis of functionalized 2-amino-4H-pyrans from β-dicarbonyl compounds, malononitrile, and aldehydes is presented. Good to excellent yields were obtained under mild reaction condition and with short reaction times by using magnetite-supported graphitic carbon nitride as a truly recyclable catalyst. This efficient and simple technique avoids the use of solvent extraction and column chromatography. In addition, the catalyst can be easily and effectively recovered and reused several times without significant loss of its catalytic activity.

Key words

pyrans - multicomponent reactions - graphitic carbon nitride - ferrite - catalyst support - green chemistry

• References and Notes

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• 13 4H-Pyrans; General Procedure A mixture of the appropriate aldehyde 1 (1.0 mmol), malononitrile (2; 1.0 mmol), 1,3-dicarbonyl compound 3 (1.0 mmol), and Fe₃O₄@g-C₃N₄ (20 mg) in EtOH (1 mL) was stirred at 60 °C for 60 min until the reaction was complete (TLC). EtOH (10 mL) was added, and the Fe₃O₄@g-C₃N₄ was separated with an external magnet. The crude product was then crystallized from EtOH. 2-Amino-7,7-dimethyl-5-oxo-4-phenyl-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile (4a) Colorless crystals; yield: 143 mg (97%); mp 228–230 °C. ¹H NMR (CDCl₃, 500 MHz): δ = 7.38–7.00 (m, 7 H, PhH and NH₂), 4.30 (s, 1 H), 5.23 (s, 2 H), 2.39 (m, 2 H), 2.13–2.15 (m, 2 H), 1.03 (s, 3 H), 0.98 (s, 3 H). ¹³C NMR (CDCl₃, 125 MHz): δ = 196.8, 162.8, 157.9, 144.3, 129.5, 128.8, 127.9, 118.8, 114.7, 61.9, 51.6, 35.9, 33.0, 29.6, 28.1.
• 14 Preparation of the magnetic g-C₃N₄ catalyst A g-C₃N₄ nanosheet was prepared by directly calcining melamine in air. An alumina crucible with a loose cover containing melamine (2.0 g) was placed in a muffle furnace, and the temperature was programmed to 550 °C for 5 h at an initial ramp rate of 5 °C/min. After heat treatment, bulk g-C₃N₄ was obtained as a pale-yellow powder (see Ref. 10a). This bulk g-C₃N₄ (1.0 g) was added to a second alumina crucible, which was heated at 550 °C for 2 h, with initial heating at a rate of 10 °C/min, to obtain white g-C₃N₄ nanosheets. In the final step, Fe₃O₄@g-C₃N₄ was prepared by the reported method (Ref. 10). The g-C₃N₄ (500 mg) was dispersed in 1:1 EtOH–H₂O by sonication at r.t. FeCl₃·6H₂O (1.838 g, 0.0216 mol) and FeCl₂·4H₂O (0.703 g, 0.0108 mol) were dissolved in the dispersion by sonication for 30 min, and then 28% aq NH₃ (10 mL) was rapidly added to the stirred solution. The mixture was stirred under N₂ for 30 min at 80 °C, then cooled to r.t. The solid was separated magnetically, washed with H₂O and EtOH, and dried overnight at 60 °C under vacuum.