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Synlett 2012; 23(15): 2209-2214
DOI: 10.1055/s-0032-1317014
DOI: 10.1055/s-0032-1317014
letter
A Greener Protocol for Accessing 2,3-Dihydro/spiroquinazolin-4(1H)-ones: Natural Acid-SDS Catalyzed Three-Component Reaction
Further Information
Publication History
Received: 13 April 2012
Accepted after revision: 09 July 2012
Publication Date:
14 August 2012 (online)
Abstract
A novel green and energy-efficient synthesis of 2,3-dihydro/spiroquinazolin-4(1H)-ones via three-component cyclocondensation reaction involving isatoic anhydride, amines and aldehydes/ketones utilizing recyclable tartaric acid–SDS catalyst system has been achieved. With simple requirements of mechanical stirring or mechanochemical activation at room temperature and one of the shortest reported times as of yet, it is a significant improvement on previously described methods for the synthesis of such compounds. Moreover the catalyst system can also be efficiently applied in large-scale reactions which indicates the potential for applications in industry.
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- 10 Representative Procedure: Method A: In a round-bottom flask, isatoic anhydride (0.1 g, 0.61 mmol) and amine (0.61 mmol) were dissolved in micellar solution of H2O–EtOH (3:1; 4 mL) sensitized with SDS (20 mol%). Tartaric acid (0.92 g, 0.61 mmol) and aldehyde/ketone (0.61 mmol) were then successively added and the reaction was allowed to stir at r.t. for an appropriate time indicated in Tables 2–4. The solid precipitate was filtered, washed with H2O, dried and could be used without further purification, however in case of 4r, 4s and 4t recrystallization with EtOH–ice was required. Method B: isatoic anhydride (0.1 g, 0.61 mmol) and amine (0.61 mmol) were mixed with a few drops of the solvent system (H2O–EtOH, 3:1) in a mortar. Tartaric acid (0.92 g, 0.61 mmol), SDS (20 mol%) and aldehyde/ketone (0.61 mmol) were then successively added and ground together with a pestle until completion of the reaction (Tables 2–4). In most of the cases the product was washed with H2O, however in case of 4r–t recrystallization with EtOH–ice was required. 3-Butyl-2-phenyl-2,3-dihydroquinazolin-4(1H)-one (4a): colorless solid; yield: 0.15 g (87%); mp 132–135 °C. 1H (300 MHz, CDCl3): δ = 7.88 (d, 1 H, J = 6.9 Hz), 7.21 (br s, 4 H), 7.13–7.19 (m, 2 H), 6.76 (t, 1 H, J = 7.3 Hz), 6.44 (d, 1 H, J = 8.0 Hz), 5.76 (s, 1 H), 3.85–3.94 (m, 1 H), 2.64–2.74 (m, 1 H), 1.45–1.49 (m, 2 H), 1.20–1.27 (m, 2 H), 0.80 (t, 3 H, J = 7.3 Hz).13C (50 MHz, CDCl3): δ = 163.2, 145.2, 140.0, 133.4, 129.2, 128.9, 128.4, 126.5, 119.1, 116.2, 114.4, 72.1, 44.6, 29.8, 20.2, 13.8. IR (KBr): 3360, 1634 cm–1. MS (ES+): m/z = 281.1 [M+ + 1]. HRMS (DART): m/z calcd for [C18H20N2O + H+]: 281.1654; found: 281.1647. 3-Butyl-2-ferrocenyl-2,3-dihydroquinazolin-4(1H)-one (4q): yellow solid; yield: 0.17 g (72%); mp 137–140 °C. 1H NMR (300 MHz, CDCl3): δ = 7.83 (d, 1 H, J = 7.4 Hz), 7.19–7.27 (m, 1 H), 6.79 (t, 1 H, J = 7.4 Hz), 6.64 (d, 1 H, J = 6.9 Hz), 5.40 (s, 1 H), 4.08–4.21 (m, 10 H), 3.75–3.79 (m, 1 H), 2.88–2.92 (m, 1 H), 1.42–1.50 (m, 2 H), 1.19–1.28 (m, 2 H), 0.82 (t, 3 H, J = 7.5 Hz). 13C NMR (50 MHz, CDCl3): δ = 162.7, 146.4, 133.3, 128.7, 119.3, 116.5, 113.9, 88.6, 73.3, 69.1, 68.81, 68.76, 68.6, 68.2, 66.3, 44.0, 30.1, 20.3, 14.0. IR (KBr): 3285, 1631 cm–1. MS (ES+) m/z = 389.0 [M+ + 1]. HRMS (DART): m/z calcd for [C22H24FeN2O + H+]: 389.1316; found: 389.1318. 2,3-Diphenyl-2,3-dihydroquinazolin-4(1H)-one (4t): colorless solid; yield: 0.14 g (74%); mp 212–214 ºC. 1H NMR (300 MHz, CDCl3): δ = 8.04 (d, 1 H, J = 7.8 Hz), 7.19–7.38 (m, 11 H), 6.92 (t, 1 H, J = 7.5 Hz), 6.65 (d, 1 H, J = 7.8 Hz), 6.11 (s, 1 H). 13C NMR (75 MHz, CDCl3 + CD3OD): δ = 165.6, 147.8, 142.1, 141.6, 135.8, 130.6, 130.5, 130.2, 128.7, 128.4, 120.5, 117.5, 116.5, 76.2. IR (KBr): 3327, 1649 cm–1. MS (ES+): m/z = 301.1 [M+ + 1]. HRMS (DART): m/z calcd for [C20H16N2O + H+]: 301.1335; found: 301.1333. 2-Phenyl-2,3-dihydroquinazolin-4(1H)-one (4u): colorless solid; yield: 0.12 g (89%); mp 218–220 ºC. 1H NMR (200 MHz, CDCl3): δ = 7.96 (d, 1 H, J = 8.1 Hz), 7.26–7.58 (m, 6 H), 6.94 (t, 1 H, J = 7.2 Hz), 6.69 (d, 1 H, J = 8.0 Hz), 5.90 (s, 1 H), 5.82 (s, 1 H, NH), 4.41 (s, 1 H, NH). 13C NMR (75 MHz, CDCl3): δ = 169.5, 152.9, 145.8, 138.4, 133.8, 133.3, 132.6, 132.0, 122.6, 119.8, 119.5, 72.5. IR (KBr): 3296, 3190, 1656 cm–1. MS (ES+): m/z = 225.0 [M+ + 1]. HRMS (DART): m/z calcd for [C14H12N2O + H+]: 225.1022; found: 225.1017. 1′H-Spiro[cyclohexane-1,2′-quinazolin]-4′(3′H)-one (4v): colorless solid; yield: 0.09 g (71%); mp 217–219 °C.1H NMR (200 MHz, CDCl3): δ = 7.89 (dd, 1 H, J 1 = 7.8 Hz, J 2 = 1.2 Hz), 7.28–7.33 (m, 1 H), 6.84 (t, 1 H, J = 7.5 Hz), 6.67 (d, 1 H, J = 7.8 Hz), 6.43 (s, 1 H, NH), 4.40 (s, 1 H, NH), 1.84 (br s, 4 H), 1.47–1.68 (m, 6 H). 13C NMR (75 MHz, CDCl3 + CD3OD): δ = 167.0, 148.0, 136.2, 130.3, 120.7, 117.0, 70.5, 39.7, 26.8, 24.0. IR (KBr): 3362, 3179, 1647 cm–1. MS (ES+): m/z = 217.0 [M+ + 1]. HRMS (DART): m/z calcd for [C13H16N2O + H+]: 217.1335; found: 217.1326. 1-Ethyl-1′H-spiro[indoline-3,2′-quinazoline]-2,4′(3′H)-dione (4x): tan solid; yield: 0.15 g (85%); mp 227–230 °C. 1H NMR (300 MHz, DMSO-d 6): δ = 8.29 (s, 1 H, NH), 7.62 (d, 1 H, J = 7.1 Hz), 7.52 (d, 1 H, J = 7.2 Hz), 7.42 (t, 1 H, J = 7.6 Hz), 7.18–7.25 (m, 2 H), 7.00–7.16 (m, 2 H), 6.69 (t, 1 H, J = 7.3 Hz), 6.61 (d, 1 H, J = 4.0 Hz), 3.57–3.68 (m, 2 H), 1.16 (t, 3 H, J = 6.9 Hz). 13C NMR (75 MHz, DMSO-d 6): δ = 173.8, 163.9, 146.7, 142.6, 133.3, 130.9, 129.0, 126.8, 125.1, 122.7, 117.2, 114.2, 113.9, 109.0, 70.7, 34.0, 12.3. IR (KBr): 3368, 3227, 1638, 1613 cm–1. MS (ES+): m/z = 294.0 [M+ + 1]. HRMS (DART): m/z calcd for [C17H15N3O2 + H+]: 294.1164; found: 294.1156
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