Synthesis of [2,2′-Bipyridine]-1,1′-diium Tricyanomethanide as a Bifunctional Nanostructured Ionic Liquid: Application to the Synthesis of 2-Aryl-5-methyl-2,3-dihydro-1H-3-pyrazolone Derivatives

Abstract

{[2,2′-BPyH][C(CN)₃]₂} was synthesized and fully characterized by IR, ¹H NMR, ¹³C NMR, mass, X-ray diffraction patterns (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric (TG), and differential thermal (DTA) analysis. [2,2′-Bipyridine]-1,1′-diium tricyanomethanide {[2,2′-BPyH][C(CN)₃]₂} as a bifunctional nanostructure ionic liquid beneficial catalyzed the synthesis of 2-aryl-5-methyl-2,3-dihydro-1H-3-pyrazolone derivatives via the one-pot, four-component condensation reaction of aromatic aldehydes, ethyl acetoacetate, phenyl hydrazine, and β-naphthol under solvent-free conditions at room temperature. The major advantages of the offered process are efficient catalysis and recyclability of catalyst.

Key words

nanostructure ionic liquid - [2,2′-bipyridine]-1,1′-diium tricyanomethanide - 2-aryl-5-methyl-2,3-dihydro-1H-3-pyrazolone - solvent-free condition

• References and Notes

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• 32 Experimental General Procedure for the Preparation of NIL Catalyst [2,2′-Bipyridine]-1,1′-diium Tricyanomethanide {[2,2′-BPyH]-[C(CN)₃]₂} 2,2′-Bipyridine (5 mmol, 0.781 g) was added to an aq solution of tricyanomethane (5 mmol, 0.455 g, 5 mL), and the mixture was stirred at room temperature for 3 h. Consequently, the solvent was removed under reduced pressure and the brown residue was dried under vacuum at 100 °C for 3 h. A brown solid formed which was filtered, washed with Et₂O three times and then dried under vacuum. Brown solid; mp 95–97 °C; yield 96% (1.624 g). IR (KBr): ν = 3378, 3088, 3055, 2250, 1683, 1580, 1457, 1251 cm^–1. ¹H NMR (400 MHz, DMSO-d ₆): δ = 1.76 (s, 2 H, NH), 7.47 (d, 2 H, J = 6.6 Hz, ArH), 7.97 (t, 2 H, J = 8.6 Hz, ArH), 8.40 (d, 2 H, J = 8.0 Hz, ArH), 8.70 (t, 2 H, J = 7.2 Hz, ArH). ¹³C NMR (100 MHz, DMSO-d ₆): δ = 63.0, 70.0, 120.9, 124.7, 137.8, 149.7, 155.7. MS: m/z = 338 [M]⁺. General Procedure for the Synthesis of 2-Aryl-5-methyl-2,3-dihydro-1H-3-pyrazolone Derivatives To a mixture of aromatic aldehyde (1 mmol), ethyl acetoacetate (0.130 g, 1 mmol), phenylhydrazine (0.108 g, 1 mmol), and β-naphthol (0.144 g, 1 mmol) in a round-bottom flask connected to condenser, 1 mol% of {[2,2′-BPyH][C(CN)₃]₂} was added, and the resulting mixture was stirred magnetically under solvent-free conditions at room temperature for the requisite time (Table 3). After completion of the reaction as monitored by TLC (n-hexane–EtOAc = 5:2), EtOAc (10 mL) was added, the reaction mixture stirred and refluxed for 5 min, and then washed with water (10 mL) and decanted to separate catalyst from the other materials (the reaction product was soluble in hot EtOAc and the catalyst was soluble in water). The aqueous layer was decanted, separated and, after removing water, the residual catalyst could be reused. The organic layer was evaporated, and the crude product was purified by recrystallization from EtOH (for spectroscopic data of the products, see Supporting Information)