Application of {[4,4′-BPyH][C(CN)₃]₂} as a Bifunctional Nanostructured Molten Salt Catalyst for the Preparation of 2-Amino-4H-chromene Derivatives under Solvent-Free and Benign Conditions

Abstract

The bifunctional nanostructured molten salt [4,4′-bipyridine]-1,1′-diium tricyanomethanide has been employed as a highly efficient and powerful catalyst for the preparation of 2-amino-4H-chromenes. A wide variety of aromatic aldehydes was condensed with malononitrile and resorcinol, 1-naphthol or 2-naphthol under mild and solvent-free conditions. This protocol has the advantages of short reaction times, high to excellent yields, and straightforward workup.

Key words

multicomponent reactions - molten salt - ionic liquids - solvent-free conditions

• References and Notes

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• 40 General Procedure for the Preparation of Nanostructured Molten Salt {[4,4′-BPyH][C(CN)₃]₂} To an aqueous solution of tricyanomethane (0.455 g, 5 mmol, 5 mL), 4,4′-bipyridine (0.39 g, 2.5 mmol) was added and the resulting mixture was stirred for 3 h at ambient temperature. The solvent was then evaporated under reduced pressure. The pale-yellow powder was dried under vacuum at 100 °C for 3 h. The obtained pale-yellow solid was filtered, washed repeatedly with diethyl ether to remove any unreacted starting materials, and then dried under vacuum. General Procedure for the Synthesis of 2-Amino-4H-chromene Derivatives through a Cascade Knoevenagel–Michael Cyclocondensation Sequence To a mixture of aryl aldehyde (1 mmol), malononitrile (0.066 g, 1 mmol), and phenol (1 mmol) in a round-bottom flask, [4,4′-bipyridine]-1,1′-diium tricyanomethanide (3 mg) was added and the mixture was stirred at either room temperature (Table 2, entries 1–5) or 80 °C (entries 6–19) in the absence of solvent for the appropriate time (Table 2). After completion of the reaction as monitored by TLC (n-hexane/ethyl acetate, 2:1), ethyl acetate (10 mL) was added and the reaction mixture was stirred and heated to reflux for 10 min. The resulting mixture was then washed with water (10 mL) and decanted to separate catalyst from the other materials (the reaction mixture was soluble in hot ethyl acetate and nanostructured molten salt catalyst was soluble in water). The aqueous layer was decanted, separated, and the water was removed to recover the catalyst for further use. The organic layer was dried, filtered, the solvent was removed, and the crude product was purified by recrystallization from ethanol (95%) to give the pure product with high to excellent yields (Table 2). Selected Characterization Data 2-Amino-4-(4-chlorophenyl)-7-hydroxy-4H-chromene-3-carbonitrile (Table 2, Entry 1) Yield: 94% (0.280 g); mp 239–241 °C. FTIR (KBr): 3463, 3343, 3251, 2193, 1643, 1506, 1402, 1154, 1111 cm^–1. ¹H NMR (400.13 MHz, DMSO-d ₆): δ = 4.67 (s, 1 H, CH), 6.42 (d, ⁴ J = 2 Hz, 1 H, ArH), 6.50 (dd, ³ J= 8 Hz, ⁴ J = 2 Hz, 1 H, ArH), 6.79 (d, ³ J = 8 Hz, 1 H, ArH), 6.92 (s, 2 H, NH₂), 7.19 (d, ³ J = 8 Hz, 2 H, ArH), 7.37 (d, ³ J = 8 Hz, 2 H, ArH), 9.73 (s, 1 H, OH). ¹³C NMR (100.61 MHz, DMSO-d ₆): δ = 55.8, 102.2, 112.4, 113.2, 120.5, 128.5, 129.3, 129.9, 131.2, 145.3, 148.8, 157.2, 160.2. 2-Amino-4-(4-bromophenyl)-7-hydroxy-4H-chromene-3-carbonitrile (Table 2, Entry 4) Yield: 92% (0.315 g); mp 251–253 °C. FTIR (KBr): 3470, 3340, 3256, 2191, 1640, 1507, 1411, 1155, 1112 cm^–1. ¹H NMR (400.13 MHz, DMSO-d ₆): δ = 4.66 (s, 1 H, CH), 6.42 (d, ⁴ J = 2.4 Hz, 1 H, ArH), 6.50 (dd, ³ J = 8 Hz, ⁴ J = 2.4 Hz, 1 H, ArH), 6.80 (m, 1 H, ArH), 6.92 (s, 2 H, NH₂), 7.13 (d, ³ J = 8.4 Hz, 2 H, ArH), 7.50 (d, ³ J = 8.4 Hz, 2 H, ArH), 9.74 (s, 1 H, OH). ¹³C NMR (100.61 MHz, DMSO-d ₆): δ = 55.7, 102.2, 112.5, 113.1, 119.7, 120.5, 129.6, 129.9, 131.5, 145.7, 148.8, 157.2, 160.2. 2-Amino-7-hydroxy-4-(3-methoxyphenyl)-4H-chromene-3-carbonitrile (Table 2, Entry 11) Yield: 89% (0.262 g); mp 180–182 °C. FTIR (KBr): 3446, 3340, 3219, 2192, 1641, 1508, 1410, 1154, 1115, 1048 cm^–1. ¹H NMR (400.13 MHz, DMSO-d ₆): δ = 3.72 (s, 3 H, OMe), 4.59 (s, 1 H, CH), 6.41 (d, ⁴ J = 2.4 Hz, 1 H, ArH), 6.49 (dd, ³ J = 8 Hz, ⁴ J = 2.4 Hz, 1 H, ArH), 6.72–6.85 (m, 4 H, ArH), 6.87 (s, 2 H, NH₂), 7.23 (t, ³ J = 8 Hz, 1 H, ArH), 9.67 (s, 1 H, OH). ¹³C NMR (100.61 MHz, DMSO-d ₆): δ = 54.9, 56.1, 102.1, 111.5, 112.3, 113.4, 113.6, 119.5, 120.6, 129.7, 129.8, 147.9, 148.8, 157.1, 159.3, 160.3. 3-Amino-1-(4-dichlorophenyl)-1H-benzo[f]chromene-2-carbonitrile (Table 2, Entry 13) Yield: 90% (0.331 g); mp 240–242 °C. FTIR (KBr): 3463, 3324, 3190, 2200, 1661, 1589, 1407, 1237, 819 cm^–1. ¹H NMR (400.13 MHz, DMSO-d ₆): δ = 5.72 (s, 1 H, CH), 7.03 (d, ³ J = 8.4 Hz, 1 H, ArH), 7.11 (s, 2 H, NH₂), 7.27 (dd, ³ J = 8.4 Hz, ⁴ J = 2 Hz, 1 H, ArH), 7.35 (d, ³ J = 8.8 Hz, 1 H, ArH), 7.43–7.52 (m, 2 H, ArH), 7.58 (d, ³ J = 8.4 Hz, 1 H, ArH), 7.64 (d, ⁴ J = 2.4 Hz, 1 H, ArH), 7.94–7.99 (m, 2 H, ArH). ¹³C NMR (100.61 MHz, DMSO-d ₆): δ = 55.0, 114.0, 118.2, 120.5, 120.6, 122.7, 123.8, 126.3, 126.6, 126.7, 127.6, 128.7, 132.6, 137.8, 142.6, 158.1, 159.9. 2-Amino-4-(4-methoxyphenyl)-4H-benzo[h]chromene-3-carbonitrile (Table 2, Entry 16) Yield: 90% (0.296 g); mp 188–190 °C. FTIR (KBr): 3415, 3324, 2194, 1663, 1604, 1509, 1377, 1253, 1104, 1023, 809 cm^–1. ¹H NMR (400.13 MHz, DMSO-d ₆): δ = 3.72 (s, 3 H, OMe), 4.85 (s, 1 H, CH), 6.88 (d, ³ J = 8.4 Hz, 2 H, ArH), 7.10 (m, 1 H, NH₂ and 1 H, ArH), 7.17 (d, ³ J = 8.4 Hz, 2 H, ArH), 7.56–7.66 (m, 4 H, ArH), 7.89 (d, ³ J = 8 Hz, 1 H, ArH), 8.24 (d, ³ J = 8 Hz, 1 H, ArH). ¹³C NMR (100.61 MHz, DMSO-d ₆): δ = 34.8, 55.7, 114.1, 116.8, 119.7, 122.5, 125.1, 127.5, 128.5, 128.7, 128.9, 129.9, 130.1, 130.8, 131.4, 131.9, 132.1, 141.7, 147.1, 159.8.