ZnO-Nanoparticles-Catalyzed Synthesis of Poly(tetrahydrobenzimidazo[2,1-b]quinazolin-1(2H)-ones) as Novel Multi-armed Molecules

Dedicated to Professor Klaus Hafner on the occasion of his 90th birthday

Abstract

A new series of poly(tetrahydrobenzimidazo[2,1-b]-quinazolin-1(2H)-ones) was synthesized in good yields using a multicomponent reaction of poly(aldehydes), dimedone, and 2-aminobenzimidazole in DMF under conventional heating as well as under microwave irradiation.

Key words

poly(aldehydes) - 2-aminobenzimidazole - cyclocondensation - Michael addition - poly(alkylation) - poly(tetrahydrobenzimidazoquinazolinone)

• References and Notes

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• 79 Compound 7 was obtained by heating a mixture of 4-formylbenzoic acid (11, 1 mmol), dimedone (2, 1 mmol), and aminobenzimidazole (3, 1 mmol) in DMF (10 mL) at reflux for 1 h. The crude solid was isolated and recrystallized from DMF as colorless crystals (82%); mp > 300 °C. ¹H NMR (300 MHz, DMSO-d₆ ): δ = 0.91 (s, 3 H, CH₃), 1.06 (s, 3 H, CH₃), 2.02–2.23 (m, 2 H, CH₂), 2.61–2.67 (m, 2 H, CH₂), 6.49 (s, 1 H, H12), 6.95–7.95 (m, 8 H, Ar-H), 11.60–12-81 (br, 2 H, NH, COOH). MS (EI): m/z = 387 [M]⁺. Anal. Calcd for C₂₃H₂₁N₃O₃: C, 71.30; H, 5.46; N, 10.85. Found: C, 71.43; H, 5.38; N, 10.63.
• 80 Typical Experimental Procedure for the Synthesis of Poly(aldehydes) 13, 15, 17 and 23 To a stirred solution of 4-formylbenzoic acid (11) in ethanol (10 mL), KOH (3, 4, or 6 mmol) was added. The reaction mixture was stirred at room temperature for 10 min. The solvent was then removed in vacuo, and the remaining solid was triturated with dry diethyl ether, collected, and dried to give the corresponding potassium salts. A solution of the latter salts (3, 4, or 6 mmol) and the corresponding poly(bromo) compounds (1 mmol) in DMF (20 mL) was heated under reflux for 5 min during which time KBr was precipitated. The solvent was then removed in vacuo, and the remaining material was washed with water (50 mL) and crystallized from the proper solvents to give the corresponding poly(aldehydes). Compound 13: colorless crystals (butanol, 76%); mp >300 °C. IR (KBr): ν = 1714 (br, 2 CO) cm^–1. ¹H NMR (DMSO-d ₆): δ = 5.46 (s, 6 H, 3-OCH₂), 7.59 (s, 3 H, Ar-H), 7.98–8.17 (m, 12 H, Ar-H), 10.10 (s, 3 H, 3-CHO). ¹³C NMR (DMSO-d ₆): δ = 66.1, 126.8, 129.5, 129.8, 134.1, 136.7, 139.1, 164.7, 192.7. MS (EI): m/z = 564 [M]⁺. Anal. Calcd for C₃₃H₂₄O₉: C, 70.21; H, 4.29. Found: C, 70.18; H, 4.06. Compound 15: colorless crystals (dioxane, 83%); mp 200–204 °C. IR (KBr): ν = 1724, 1701 (2 CO) cm^–1. ¹H NMR (300 MHZ, DMSO-d ₆): δ = 5.59 (s, 8 H, 4-OCH₂), 7.81–8.05 (m, 18 H, Ar-H), 10.03 (s, 4 H, 4- CHO). MS (EI): m/z = 726 [M]⁺. Anal. Calcd for C₄₂H₃₀O₁₂: C, 69.42; H, 4.16. Found: C, 69.53; H, 4.09.
• 81 Typical Experimental Procedure for the Synthesis of the Polypodal Compounds 9, 10, 18–21, 24, and 25 To a solution of the appropriate poly(aldehydes) (1 mmol) in DMF (10 mL), dimedone (2, 3, 4, or 6 mmol), aminobenzimidazole (3, 3, 4, or 6 mmol), and ZnO nanocatalyst (10 mol%) were added. The reaction mixture was heated at reflux for 1 h (method A) or irradiated in a focused microwave reactor for 15 min at 160 °C (250 W; method B). The crude solid was isolated and recrystallized from DMF/ethanol. Compound 9: pale yellow crystals, (method A, 85%; method B, 88%); mp >300 °C. ¹H NMR (DMSO-d ₆): δ = 0.93 (s, 9 H, 3 CH₃), 1.05 (s, 9 H, 3 CH₃), 2.02–2.27 (m, 6 H, 3 CH₂), 2.54–2.59 (m, 6 H, 3 CH₂), 4.95 (s, 6 H, 3-OCH₂), 6.35 (s, 3 H, H12), 6.81–7.36 (m, 27 H, Ar-H), 11.02 (br, 3 H, NH). ¹³C NMR (DMSO-d ₆): δ = 26.7, 28.6, 32.2, 50.0, 53.5, 69.0, 106.5, 110.0, 114.4, 116.9, 120.3, 121.7, 126.3, 128.1, 131.9, 134.0, 137.4, 141.9, 145.4, 150.0, 157.7, 192.5. Anal. Calcd for C₇₅H₆₉N₉O₆: C, 75.54; H, 5.83; N, 10.57. Found: C, 75.43; H, 5.77; N, 10.50. Compound 10: pale yellow crystals, (method A, 89%; method B, 89%); mp >300 °C. IR (KBr): ν = 3230 (NH), 1722, 1647 (2CO) cm^–1. ¹H NMR (DMSO-d ₆): δ = 0.90 (s, 9 H, 3 CH₃), 1.05 (s, 9 H, 3 CH₃), 2.07–2.28 (m, 6 H, 3 CH₂), 2.55–2.61 (m, 6 H, 3 CH₂), 5.27 (s, 6 H, 3-OCH₂), 6.52 (s, 3 H, H12), 6.92–7.85 (m, 27 H, Ar-H),11. 2 (br, 3 H, NH). ¹³C NMR (DMSO-d ₆) : δ = 26.5, 28.5, 32.1, 49.8, 53.9, 65.6, 105.5, 109.7, 116.9, 120.4, 121.8, 126.7, 127.3, 128.7, 129.2, 131.7, 136.7, 141.8, 145.1, 146.5, 150.5, 164.9, 192.4. Anal. Calcd for C₇₈H₆₉N₉O₉: C, 73.39; H, 5.45; N, 9.88. Found: C, 73.51; H, 5.61; N, 9.92.
• 82 The IR spectra were recorded on potassium bromide disks on a PyeUnicam SP3-300 and Shimadzu FTIR 8101 PC infrared spectrophotometer. The ¹H NMR and ¹³C NMR spectra were determined on a Varian Mercury VX 300 NMR spectrometer using TMS as an internal standard and DMSO-d ₆ as a solvent. Mass spectra were measured on a GCMSQP1000 EX spectrometer at 70 eV. Elemental analyses were carried out at the Microanalytical Center of Cairo University, Giza, Egypt. ZnO NPs were used as purchased from Sigma-Aldrich. Characterization of ZnO NPs was provided as Supplementary Data.