Magnetic Metal–Organic Framework CoFe₂O₄@SiO₂@IRMOF-3 as an Efficient Catalyst for One-Pot Synthesis of Functionalized Dihydro-2-oxopyrroles

Abstract

A magnetic metal–organic framework-based catalyst CoFe₂O₄@SiO₂@IRMOF-3 was prepared and identified as an efficient catalyst for the synthesis of a variety of functionalized dihydro-2-oxopyrroles by a one-pot, four-component reaction of a dialkyl acetylenedicarboxylate, an aryl amine, formaldehyde, and optionally a second amine or diamine at room temperature. The catalyst was magnetically separated and recovered without significant loss of its catalytic efficiency, even after eight reaction cycles.

Key words

magnetic separation - metal–organic framework - nanostructures - multicomponent reactions - dihydropyrroles - cobalt catalysis

• References and Notes

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• 46 Magnetic CoFe₂O₄@SiO₂@IRMOF-3 Nanoparticles CoFe₂O₄ magnetic nanoparticles (NPs) were synthesized by chemical co-precipitation from FeCl₃·6H₂O and CoCl₂·6H₂O. The surface of the CoFe₂O₄ NPs was coated with a layer of SiO₂ by adding distilled H₂O (80 mL) to the purified CoFe₂O₄ NPs (1 g), heating for 1 h at 40 °C, adding concd aq NH₃ (1.5 mL), stirring at 40 °C for 30 min, adding TEOS (1.0 mL), and stirring continuously for 24 h. The mixture was then cooled to r.t. and the silica-coated NPs were collected by using a permanent magnet, washed three times with distilled H₂O and EtOH, and dried at 60 °C under vacuum for 6 h. A versatile step-by-step assembly strategy was used to fabricate the porous CoFe₂O₄@SiO₂@IRMOF-3 core–shell nanoparticles. Briefly, the CoFe₂O₄@SiO₂ NPs (0.5 g) were dispersed in a solution of Zn(NO₃)₂ (1.7 g) and H₂NH₂BDC (0.4 g) in dry DMF (50 mL), and the mixture was stirred at r.t. for 20 min. The solution was then transferred to a Teflon-lined steel autoclave, which was sealed and kept at 100 °C for 20 h. The resulting brown solid was collected with a permanent magnet, washed with EtOH, and dried under vacuum at 60 °C for 6 h.
• 47 Pyrrolidinones 4a–h; General Procedure A mixture of the dialkyl acetylenedicarboxylate 1 (1 mmol), aromatic amine 2 (2 mmol), 37% aq HCHO (3, 5 mmol), and CoFe₂O₄@SiO₂@IRMOF-3 (0.02 g) in MeOH (3 mL) was stirred at r.t. for the appropriate time (Table 2). When the reaction was complete (TLC), the catalyst was separated by using a bar magnet, and the product was collected by filtration and washed with EtOH. Methyl 1-(2-Bromophenyl)-4-[(2-bromophenyl)amino]-5-oxo-2,5-dihydro-1H-pyrrole-3-carboxylate (4f)White solid; yield: 482 mg (82%); mp 165–166 °C. IR (KBr): 3330, 1686, 1635, 1446, 1298, 825 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 3.80 (s, 3 H), 4.48 (s, 2 H), 7.03 (t, J = 7.5 Hz, 1 H), 7.18 (t, J = 7.0 Hz, 1 H), 7.33–7.36 (m, 5 H), 7.49–7.51 (m, 1 H), 8.40 (s, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 49.7, 51.5, 106.7, 124.3, 125.1, 126.4, 126.5, 127.8, 129.2, 129.6, 129.7, 130.6, 132.4, 135.0, 135.4, 142.6, 164.1, 165.0. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₈H₁₄Br₂N₂O₃: 464.9449; found: 464.9455.
• 48 Pyrrolidinones 6a–p and Bipyrrolidinones 8a–e; General ProcedureA mixture of the aromatic amine 3 (1 mmol for product 6; 2 mmol for product 8) and dialkyl acetylenedicarboxylate (1 mmol for product 6; 2 mmol for product 8) in MeOH (3 mL) was stirred at r.t. for 20 min. Amine 5 (1 mmol) or propane-1,3-diamine (7, 1 mmol), 37% aq HCHO (1.5 mmol for product 6; 3.0 mmol for product 8), and CoFe₂O₄@SiO₂@IRMOF-3 (0.02 g) were added successively, and the mixture was stirred at r.t. for the appropriate time (Tables 3 and 4). When the reaction was complete (TLC), the catalyst was separated with a bar magnet, and the product was collected by filtration and washed with EtOH.Methyl 1-(4-Methoxyphenyl)-5-oxo-4-(phenylamino)-2,5-dihydro-1H-pyrrole-3-carboxylate (6a)White solid; yield: 273 mg (81%); mp 120–121 °C. IR (KBr): 3279, 1711, 1688, 1510, 1201, 823 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 3.74 (s, 3 H), 3.80 (s, 3 H), 4.49 (s, 2 H), 6.84–6.86 (m, 1 H), 6.91 (d, J = 9.0 Hz, 2 H), 7.09 (d, J = 8.5 Hz, 1 H), 7.13–7.15 (m, 1 H), 7.28–7.32 (m, 2 H), 7.64–7.67 (m, 2 H), 8.02 (s, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 48.7, 51.3, 55.5, 100.8, 113.6, 114.3, 119.3, 121.1, 122.8, 124.6, 125.1, 128.3, 157.1, 163.5, 165.1. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₉H₁₉N₂O₄: 339.1345; found: 339.1353.Methyl 1-(4-Bromophenyl)-4-(cyclopentylamino)-5-oxo-2,5-dihydro-1H-pyrrole-3-carboxylate (6m)White solid; yield: 336 mg (89%); mp 90–92 °C. IR (KBr): 3335, 1713, 1683, 1259, 844 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 1.45–1.50 (m, 2 H), 1.60–1.65 (m, 3 H), 1.71–1.75 (m, 2 H), 2.02–2.07 (m, 2 H), 3.78 (s, 3 H), 4.37 (s, 2 H), 5.03 (s, 1 H), 7.49-7.51 (m, 2 H), 7.67–7.69 (m, 2 H). ¹³C NMR (125 MHz, CDCl₃): δ = 23.7, 34.8, 47.8, 50.9, 54.1, 95.9, 117.7, 120.5, 128.8, 132.0, 137.9, 164.4, 165.5. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₇H₂₀BrN₂O₃: 379.0657; found: 379.0661.Dimethyl 4,4'-[Propane-1,3-diylbis(azanediyl)]bis(5-oxo-1-phenyl-2,5-dihydro-1H-pyrrole-3-carboxylate) (8a)White solid; yield: 445 mg (89%); mp 104–105 °C. IR (KBr): 3314, 2950, 1706, 1686, 1499, 1259, 762 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 1.92–1.97 (m, 2 H), 3.78 (s, 6 H), 3.97–4.01 (m, 4 H), 4.39 (s, 4 H), 7.10 (t, J = 7.5 Hz, 2 H), 7.37 (t, J = 8.0 Hz, 4 H), 7.74 (d, J = 8.0 Hz, 4 H). ¹³C NMR (125 MHz, CDCl₃): δ = 33.2, 40.3, 48.0, 51.0, 118.2, 119.4, 125.0, 129.1, 129.3, 138.8, 164.5, 165.5. HRMS (ESI): m/z [M + H]⁺ calcd for C₂₇H₂₉N₄O₆: 505.2087; found: 505.2093.Dimethyl 4,4'-[Propane-1,3-diylbis(azanediyl)]bis[5-oxo-1-(p-tolyl)-2,5-dihydro-1H-pyrrole-3-carboxylate] (8c)White solid; yield: 479 mg (90%); mp 135–136 °C. IR (KBr): 3401, 2951, 1659, 1636, 1455, 1258, 820 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 1.93–1.95 (m, 2 H), 2.34 (s, 6 H), 3.77 (s, 6 H), 3.97–4.01 (m, 4 H), 4.36 (s, 4 H), 7.17 (d, J = 8.5 Hz, 4 H), 7.60 (d, J = 8.5 Hz, 4 H). ¹³C NMR (125 MHz, CDCl₃): δ = 20.9, 29.7, 40.0, 47.4, 51.0, 119.4, 129.6, 129.7, 132.4, 134.7, 136.3, 161.9, 164.3. HRMS (ESI): m/z [M + H]⁺ calcd for C₂₉H₃₃N₄O₆: 533.2400; found: 533.2406.4,4'-[Propane-1,3-diylbis(azanediyl)]bis[1-(4-bromophenyl)-5-oxo-2,5-dihydro-1H-pyrrole-3-carboxylate] (8e)Yellow solid; yield: 574 mg (87%); mp 168–170 °C. IR (KBr): 3324, 2941, 1703, 1687, 1645, 1430, 1290, 1200, 759 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 1.87–1.90 (m, 2 H), 3.73 (s, 6 H), 3.93-3.95 (m, 4 H), 4.28 (s, 4 H), 7.40–7.45 (m, 4 H), 7.59 (d, J = 9.0 Hz, 4 H). ¹³C NMR (125 MHz, CDCl₃): δ = 33.0, 40.1, 47.8, 51.1, 117.7, 119.3, 119.6, 120.5, 132.0, 137.8, 164.5, 165.5. HRMS (ESI): m/z [M + H]⁺ calcd for C₂₇H₂₇Br₂N₄O₆: 661.0297; found: 661.0292.